CN102099750A

CN102099750A - Electrophotographic photoreceptor, process cartridge, and electrophotographic apparatus

Info

Publication number: CN102099750A
Application number: CN2009801282040A
Authority: CN
Inventors: 大垣晴信; 植松弘规; 大地敦
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 2008-07-18
Filing date: 2009-07-16
Publication date: 2011-06-15
Anticipated expiration: 2029-07-16
Also published as: KR20110028546A; WO2010008095A1; US20100092208A1; WO2010008094A1; EP2306248A4; JPWO2010008094A1; US7901855B2; CN102099751B; KR101196105B1; JPWO2010008095A1; CN102099750B; JP5264762B2; JP4795469B2; US7875410B2; KR20110028655A; KR101317070B1; EP2306247A4; US20100092209A1; EP2306248B1; EP2306247B1

Abstract

Disclosed is an electrophotographic photoreceptor that can continually exhibit the effect of relaxing stress of contact with a contact member or the like and, at the same time, has an excellent potential stability during repeated use. Also disclosed are a process cartridge comprising the electrophotographic photoreceptor, and an electrophotographic apparatus. The electrophotographic photoreceptor comprises a charge transport layer as a surface layer. The charge transport layer comprises a polyester resin as a binder resin. The polyester resin has a repeating structural unit represented by formula (1) and a repeating structural unit represented by formula (2). The content of siloxane sites in the polyester resin is 5 to 30% by mass based on the total mass of the polyester resin, and the content of the polyester resin in the charge transport layer is not less than 60% by mass of the total mass of the whole binding resin in the charge transport layer.

Description

Electrophotographic photosensitive element, handle box and electronic photographing device

Technical field

The present invention relates to electrophotographic photosensitive element, have the handle box and the electronic photographing device of electrophotographic photosensitive element.

Background technology

Recently, the photoconductivity material (charge generation material and charge transport material) as the electrophotographic photosensitive element that is used for being installed in electronic photographing device has carried out the exploitation of organic photoconductive material energetically.

Use the electrophotographic photosensitive element (electrophotographic Electrifier frame, photoreceptor) of organic photoconductive material to have photographic layer usually, this photographic layer is by applying coating fluid and being dried formation on supporting mass, this coating fluid is by dissolving in solvent and/or disperse organic photoconductivity material and the resin glue acquisition.In addition,, adopt laminated-type (along stratotype) usually as the layer structure of photographic layer, its by with charge generation layer and charge transport layer according to this order be stacked on the supporting mass continuously and form.

Use the electrophotographic photosensitive element of organic photoconductive material always not satisfy desired all characteristics of electrophotographic photosensitive element with high level.In xerography, various members for example developer, charging member, cleaning balde, paper and transfer member (hereinafter being also referred to as " contact member ") contact with the electrophotographic photosensitive element surface.As the required characteristic of electrophotographic photosensitive element, can mention and reduce the image degradation that causes owing to contact stress with these contact members.Especially, along with the permanance improvement of electrophotographic photosensitive element in recent years, expectation is kept and is reduced because the effect of the image degradation that contact stress causes.

About alleviating contact stress, the silicone-modified resin that has proposed in strand, to have siloxane structure be added into will with the superficial layer of contact member contacting electronic photosensitive member.For example, Japanese Patent Application Laid-Open H11-143106 (patent documentation 1) and Japanese Patent Application Laid-Open 2007-199688 (patent documentation 2) disclose and have had the resin that is introduced into the siloxane structure in the polycarbonate resin.Japanese Patent Application Laid-Open H03-185451 (patent documentation 3) discloses has the resin that is introduced into the siloxane structure in the vibrin.Japanese Patent Application Laid-Open H11-194522 (patent documentation 4) discloses the resin with the annular siloxane structure that is introduced in the vibrin.Japanese Patent Application Laid-Open 2000-075533 (patent documentation 5) discloses the resin with the branched silicone structure that is introduced into wherein.Japanese Patent Application Laid-Open 2002-128883 (patent documentation 6) discloses the resin that has at the terminal siloxane structure of introducing of vibrin.Japanese Patent Application Laid-Open 2003-302780 (patent documentation 7) discloses the technology that vibrin that will have siloxane structure and the compound with polymerism functional group are added into the superficial layer of electrophotographic photosensitive element.

Yet disclosed polycarbonate resin in

patent documentation

1 and 2 is compared bad mechanical strength with vibrin, particularly aromatic polyester resins.Therefore, improve in order to satisfy recently required permanance evenly, they may be not enough.In addition, in

patent documentation

1 and 2 disclosed resins, when being used in combination the polytype resin in superficial layer, the polycarbonate resin with introducing siloxane structure wherein migrates to the surface of superficial layer.At the initial stage of using electrophotographic photosensitive element, this is the effective ways that relax contact stress; Yet from the angle of effect continuation, this method may be not enough.

What comprise in charge transport layer in addition, is one of to have in the material of high electrofax characteristic as the compound with benzidine skeleton of charge transport material.Yet the compound that discloseder resins cause having the benzidine skeleton in

patent documentation

1 and 2 is assembled in resin, thereby reduces the potential stability during reusing.

In addition, disclosed vibrin is the resin that the block copolymerization by siloxane structure and aromatic polyester structure obtains in patent documentation 3.Yet the charge transport material is tending towards assembling in this resin, reduces the potential stability during reusing.

In addition, the physical strength of disclosed resin is good in patent documentation 4; Yet the effect that relaxes contact stress may be insufficient.

In addition, disclosed resin is good aspect the mitigation contact stress in patent documentation 5; Yet, in some cases, the charge transport material be tending towards in resin assembling and reuse during potential stability may reduce.

In addition, in the disclosed resin, the effect that relaxes contact stress is insufficient in patent documentation 6.In addition, when being used in combination various kinds of resin in superficial layer, disclosed resin is tending towards migrating to the surface of superficial layer in patent documentation 6.Therefore, from the angle of effect continuation, it is not enough.

In addition, from relaxing the angle of contact stress, disclosed resin is not enough in patent documentation 7, and in addition, in some cases, the charge transport material is tending towards assembling in resin and potential stability reduction during reusing.

Summary of the invention

The object of the present invention is to provide electrophotographic photosensitive element, it is also good with the effect and the potential stability during the repeated use of the contact stress of contact member that described electronics Electrifier frame, photoreceptor can continue to bring into play mitigation, and handle box and the electronic photographing device with electrophotographic photosensitive element is provided.

The invention provides and have supporting mass, be arranged at the charge generation layer on the described supporting mass and contain charge transport material and resin glue and be formed at the electrophotographic photosensitive element of the charge transport layer on the described charge generation layer, described charge transport layer is as the superficial layer of electrophotographic photosensitive element, wherein: described charge transport layer contain have by the constitutional repeating unit of following formula (1) expression and by the vibrin of the constitutional repeating unit of following formula (2) expression as resin glue, gross mass with respect to vibrin, the content at siloxane position is for being not less than 5 quality % to being not more than 30 quality % in the described vibrin, with gross mass with respect to whole resin glues in the charge transport layer, the content of vibrin is for being not less than 60 quality % in the described charge transport layer

Wherein, in formula (1), X ¹The expression divalent organic group; R ¹And R ²Represent replacement or unsubstituted alkyl or replacement or unsubstituted aryl independently of one another; Z represents to have more than 1 replacement or the unsubstituted alkylidene to 4 following carbon atoms; With n represent the repetition average of bracket inner structure, scope be more than 20 to below 80,

Wherein, in formula (2), R ¹¹To R ¹⁸Represent hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl or replacement or unsubstituted alkoxy independently of one another; X ²The expression divalent organic group; Represent singly-bound, replacement or unsubstituted alkylidene, replacement or unsubstituted arlydene, oxygen atom or sulphur atom with Y.

In addition, the invention provides a kind of handle box, at least a device that it comprises above-mentioned electrophotographic photosensitive element and is selected from the group of being made up of charging device, developing apparatus, transfer device and cleaning device, wherein said electrophotographic photosensitive element and described at least a device are supported integratedly and removably are mounted to the main body of electronic photographing device.

In addition, the invention provides a kind of electronic photographing device with above-mentioned electrophotographic photosensitive element, charging device, exposure device, developing apparatus and transfer device.

According to the present invention, can provide to continue to bring into play and relax with the effect of the contact stress of contact member and the good electrophotographic photosensitive element of potential stability during reusing, and handle box and the electronic photographing device with described electrophotographic photosensitive element is provided.

With reference to the accompanying drawings, from the description of following exemplary, further feature of the present invention will be apparent.

Description of drawings

Fig. 1 is the figure that schematically shows by the crimping shape transferred thereon/process equipment of mould.

Fig. 2 schematically shows another figure by the crimping shape transferred thereon/process equipment of mould.

Fig. 3 is the figure that schematically shows the electronic photographing device structure that is provided with the handle box with electrophotographic photosensitive element of the present invention.

Fig. 4 is the figure that schematically shows color electronography equipment (tandem moor (in-line the system)) structure that is provided with the handle box with electrophotographic photosensitive element of the present invention.

Fig. 5 is the figure (partial enlarged drawing) that the mold shape of using is shown among the embodiment 38 to 41, and wherein (1) be the figure of the mold shape of observing from the top and (2) be the figure of the mold shape of observation from the side.

Fig. 6 is the figure (partial enlarged drawing) that the depressed part Pareto diagram in the electrophotographic photosensitive element surface that obtains among the embodiment 38 to 41 is shown, and wherein (1) is illustrated in the ordered state of the depressed part that forms in the electrophotographic photosensitive element surface and the sectional view that (2) illustrate depressed part.

Embodiment

As mentioned above, electrophotographic photosensitive element of the present invention is to have supporting mass, be arranged at the charge generation layer on the described supporting mass and contain the charge transport material and resin glue and be formed at the electrophotographic photosensitive element of the charge transport layer on the described charge generation layer, and described charge transport layer is as superficial layer.In addition, described charge transport layer contain have by the constitutional repeating unit of following formula (1) expression and by the vibrin of the constitutional repeating unit of following formula (2) expression as resin glue.In addition, in the vibrin content at siloxane position for being not less than 5 quality % to being not more than 30 quality %, with respect to the gross mass of vibrin.In addition, the content of vibrin is not less than 60 quality % in the charge transport layer, with respect to the gross mass of whole resin glues in the charge transport layer.

In above-mentioned formula (1), X ¹The expression divalent organic group; R ¹And R ²Represent replacement or unsubstituted alkyl or replacement or unsubstituted aryl independently of one another; Z represents to have more than 1 replacement or the unsubstituted alkylidene to 4 following carbon atoms; Represent the mean value of the repeat number of bracket inner structure with n, scope is to below 80 more than 20.

In above-mentioned formula (2), R ¹¹-R ¹⁸Represent hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl or replacement or unsubstituted alkoxy independently of one another; X ²The expression divalent organic group; Represent singly-bound, replacement or unsubstituted alkylidene, replacement or unsubstituted arlydene, oxygen atom or sulphur atom with Y.

In above-mentioned formula (1), X ¹The expression divalent organic group.

As described divalent organic group, for example, can mention and replacing or unsubstituted alkylidene, replacement or unsubstituted cycloalkylidene (cycloalkylene group), replacement or unsubstituted arlydene, replacement or unsubstituted biphenylene or have the divalent group of a plurality of phenylenes via alkylidene, oxygen atom or sulfur atom linkage.In these, replace or unsubstituted alkylidene, replacement or unsubstituted arlydene, divalent group with a plurality of phenylenes via alkylidene, oxygen atom or sulfur atom linkage are preferred.

As alkylidene, can use to have more than 3 to the alkylidene that constitutes the carbon atom of main chain below 10.The example comprises propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji, inferior nonyl and inferior decyl.In these, butylidene and hexylidene are preferred.

As cycloalkylidene, can use to have more than 5 to the cycloalkylidene that constitutes the carbon atom of ring below 10.The example comprises cyclopentylene, cyclohexylidene, inferior suberyl, inferior ring octyl group, inferior ring nonyl and inferior ring decyl.In these, cyclohexylidene is preferred.

As arlydene, for example, can mention phenylene (adjacent phenylene, metaphenylene and to phenylene) and naphthylene.In these, metaphenylene and be preferred to phenylene.

As divalence phenylene, can mention adjacent phenylene, metaphenylene and to phenylene with a plurality of phenylenes via alkylidene, oxygen atom or sulfur atom linkage.In these, be preferred to phenylene.As the alkylidene that is used for a plurality of phenylenes of bonding (binding), can use to have more than 1 to the replacement or the unsubstituted alkylidene that constitute the carbon atom of main chain below 4.In these, methylene and ethylidene are preferred

As the substituting group that above-mentioned group can have, for example, can mention alkyl, alkoxy and aryl.The example of alkyl comprises methyl, ethyl, propyl group and butyl.The example of alkoxy comprises methoxyl, ethoxy, propoxyl group and butoxy.The example of aryl comprises phenyl.In these, methyl is preferred.

Now, will be in above-mentioned formula (1) X ¹Instantiation be shown in following.

In these, by above-mentioned formula (3-2), (3-4), (3-12), (3-13) and (3-18) group of expression be preferred.

In above-mentioned formula (1), X ¹It is not necessary for a kind of group.For dissolubility and the physical strength of improving vibrin, can use two or more groups as X ¹For example, using by above-mentioned formula (3-12) or (3-13) under the situation of the group of expression, from improving the angle of resin dissolves, with respect to single use, it is preferred being used in combination other group.In the time will using by the group of above-mentioned formula (3-12) expression with by the moiety combinations of above-mentioned formula (3-13) expression, the group of being represented by above-mentioned formula (3-12) in vibrin is preferably 1: 9 to 9: 1 and more preferably 3: 7 to 7: 3 with respect to the ratio (mol ratio) of the group of being represented by above-mentioned formula (3-13).

In above-mentioned formula (1), R ¹And R ²Represent replacement or unsubstituted alkyl or replacement or unsubstituted aryl independently of one another.

The example of alkyl comprises methyl, ethyl, propyl group and butyl.

The example of aryl comprises phenyl.

In these, in order to relax contact stress, R ¹And R ²Be preferably methyl.

In above-mentioned formula (1), Z represents to have more than 1 replacement or the unsubstituted alkylidene to 4 following carbon atoms.

Have more than 1 to the example of the alkylidene of 4 following carbon atoms and comprise methylene, ethylidene, propylidene and butylidene.In these, from the angle of the compatibility of vibrin and charge transport material (the opposing degree (degree of resistance) to the gathering of charge transport material vibrin is equally applicable to following), propylidene is preferred.

In above-mentioned formula (1), n represents bracket inner structure (SiR ¹R ²-O-) repetition average and scope is to below 80 more than 20.When n be more than 20 to 80 when following, the compatibility of vibrin and charge transport material increases, and can be suppressed at the gathering of charge transport material in the vibrin (resin with siloxane structure).Especially, preferred n is to below 70 more than 25.

Instantiation by the constitutional repeating unit of above-mentioned formula (1) expression will be shown in following.

In these, by above-mentioned formula (1-6), (1-7), (1-8), (1-10), (1-12), (1-13), (1-14), (1-16), (1-21) and (1-22) constitutional repeating unit of expression be preferred.

In above-mentioned formula (2), R ¹¹-R ¹⁸Represent hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl or replacement or unsubstituted alkoxy independently of one another.

As alkyl, for example, can mention methyl, ethyl, propyl group and butyl.As aryl, for example, can mention phenyl and naphthyl.As alkoxy, for example, can mention methoxyl, ethoxy, propoxyl group and butoxy.In these, from the angle of the compatibility of vibrin and charge transport material, methyl, ethyl, methoxyl, ethoxy and phenyl are preferred, and methyl is preferred.

In above-mentioned formula (2), X ²The expression divalent organic group.

As divalent organic group, can mention replacing or unsubstituted alkylidene, replacement or unsubstituted cycloalkylidene, replacement or unsubstituted arlydene, replacement or unsubstituted biphenylene or have the divalent group of a plurality of phenylenes via alkylidene, oxygen atom or sulfur atom linkage.In these, replace or unsubstituted alkylidene, replacement or unsubstituted arlydene and divalent group with a plurality of phenylenes via alkylidene, oxygen atom or sulfur atom linkage are preferred.

As alkylidene, have more than 3 to the alkylidene that constitutes the carbon atom of main chain below 10 be preferred.The example comprises propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji, inferior nonyl and inferior decyl.In these, butylidene and hexylidene are preferred.

As cycloalkylidene, have more than 5 to the cycloalkylidene that constitutes the carbon atom of ring below 10 be preferred.The example comprises cyclopentylene, cyclohexylidene, inferior suberyl, inferior ring octyl group, inferior ring nonyl and inferior ring decyl.In these, cyclohexylidene is preferred.

As the phenylene of divalent group, can mention adjacent phenylene, metaphenylene and to phenylene with a plurality of phenylenes via alkylidene, oxygen atom or sulfur atom linkage.In these, be preferred to phenylene.As the alkylidene that is used for a plurality of phenylenes of bonding, have more than 1 to the replacement or the unsubstituted alkylidene that constitute the carbon atom of main chain below 4 be preferred.In these, methylene and ethylidene are preferred

As the substituting group that aforementioned group can have separately, for example, can mention alkyl, alkoxy and aryl.As alkyl, for example, can mention methyl, ethyl, propyl group and butyl.As alkoxy, for example, can mention methoxyl, ethoxy, propoxyl group and butoxy.As aryl, for example, can mention phenyl.In these, methyl is preferred.

In above-mentioned formula (2), as X ²Instantiation, can mention and be used at above-mentioned formula (1) X ¹Those identical examples.In them, by above-mentioned formula (3-2), (3-4), (3-12), (3-13) and (3-18) group of expression be preferred.

In above-mentioned formula (2), Y represents singly-bound, replacement or unsubstituted alkylidene, replacement or unsubstituted arlydene, oxygen atom or sulphur atom.

As alkylidene, have more than 1 to the alkylidene that constitutes the carbon atom of main chain below 4 be preferred.The example comprises methylene, ethylidene, propylidene and butylidene.In these, from the angle of physical strength, methylene is preferred.

As arlydene, for example, can mention phenylene (adjacent phenylene, metaphenylene and to phenylene), biphenylene and naphthylene.

As the substituting group that above-mentioned group can have separately, for example, can mention alkyl, alkoxy and aryl.As alkyl, for example, can mention methyl, ethyl, propyl group and butyl.As alkoxy, for example, can mention methoxyl, ethoxy, propoxyl group and butoxy.As aryl, for example, can mention phenyl.

In above-mentioned formula (2), Y is preferably and replaces or unsubstituted methylene.In them, the group of being represented by following formula (5) is preferred.

In above-mentioned formula (5), R ⁵¹And R ⁵²Represent hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl or replacement or unsubstituted alkoxy independently of one another; Perhaps with R ⁵¹And R ⁵²Bonding replaces or unsubstituted ring alkylidene radical (cycloalkylidene group) or fluorenylidene (fluorenylidene group) to form.

As alkyl, for example, can mention methyl, ethyl, propyl group and butyl.In these, methyl is preferred.In addition, in the described alkyl,, for example, can mention fluoroalkyl for example trifluoromethyl and pentafluoroethyl group as the alkyl that replaces.

As aryl, for example, can mention phenyl and naphthyl.

As alkoxy, for example, can mention methoxyl, ethoxy, propoxyl group and butoxy.

As the ring alkylidene radical, for example, can mention cyclopentylidene base (cyclopentylidenegroup), cyclohexylidene base (cyclohexylidene group) and ring fork base in heptan (cycloheptylidene group).In these, it is preferred encircling and pitching base heptan.

Instantiation by the group of above-mentioned formula (5) expression is shown in following.

In these, by above-mentioned formula (5-1), (5-2), (5-3) and (5-8) group of expression be preferred.

Instantiation by the constitutional repeating unit of above-mentioned formula (2) expression is shown in following.

In these, by above-mentioned formula (2-1), (2-2), (2-8), (2-9), (2-10), (2-12), (2-17), (2-20), (2-21), (2-22), (2-24), (2-29), (2-33), (2-34) and (2-35) constitutional repeating unit of expression be preferred.

In addition, in the present invention, have by in the constitutional repeating unit of above-mentioned formula (1) expression and the vibrin by the constitutional repeating unit of above-mentioned formula (2) expression, the content that can use the siloxane position is to be not less than 5 quality % to the vibrin that is not more than 30 quality %, with respect to the gross mass of vibrin.Especially, content preferably is not less than 10 quality % to being not more than 25 quality %.

In the present invention, siloxane position (moiety) be meant contain at the silicon atom at the two ends that constitute oxyalkylene segment (portion) and be bonded to their group, by at oxygen atom, the silicon atom of the silicon atom clamping at two ends be bonded to the position of their group.More specifically, the siloxane position among the present invention for example, under the situation of the constitutional repeating unit of being represented by following formula (1-6-s), is meant the following position by dotted line that illustrates.

When the content at siloxane position with respect to have by the constitutional repeating unit of above-mentioned formula (1) expression and by the gross mass of the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression when being not less than 5 quality %, continue the effect of performance mitigation contact stress.In addition, when the content at siloxane position is not more than 30 quality %, the potential stability during being suppressed at the gathering of charge transport material in the vibrin and improving repeated use.

The content at siloxane position can pass through the general analysis methods analyst with respect to having by the constitutional repeating unit of above-mentioned formula (1) expression with by the gross mass of the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression.The example of analytical approach is shown in following.

After will being dissolved in the solvent as the charge transport layer of electrophotographic photosensitive element superficial layer, be contained in as the various materials in the charge transport layer of superficial layer by can separate with the separation equipment that reclaims component for example size exclusion chromatography (sizeexclusion chromatography) separate with high performance liquid chromatography.The vibrin of Fen Liing hydrolysis and be decomposed into carboxylic moiety and the bis-phenol part in the presence of alkali thus.The bis-phenol that obtains is partly carried out nmr analysis and mass spectrophotometry, and with the repeat number and the mol ratio thereof of calculating oxyalkylene segment, and computational ground is scaled content (mass ratio) with them.

The above-mentioned vibrin that will use is in the present invention served as reasons by the multipolymer of the constitutional repeating unit of above-mentioned formula (1) expression and the constitutional repeating unit formation by above-mentioned formula (2) expression.Copolymerized form can be in block copolymerization, random copolymerization and the alternating copolymerization any.Especially, random copolymerization is preferred.

From the angle of the permanance of the physical strength of vibrin and electrophotographic photosensitive element, the weight-average molecular weight of the above-mentioned vibrin that will use is preferably more than 80,000 and more preferably more than 90,000 in the present invention.On the other hand, from the productivity angle of dissolubility and electrophotographic photosensitive element, weight-average molecular weight is preferably below 400,000 with more preferably below 300,000.

In the present invention, the weight-average molecular weight of resin is meant the weight-average molecular weight of measuring according to conventional methods with polystyrene conversion as described below.

More specifically, resin to be measured is put into tetrahydrofuran and it was left standstill several hours.To be measured resin and tetrahydrofuran fully mixed simultaneously stirring, and make it further place 12 hour or more thereafter.Make described potpourri by sample preparation filtrator (My-Shori Disc H-25-5 by Tohso Corporation made) to obtain GPC (gel permeation chromatography) use sample thereafter.

Next, with post stabilization in 40 ℃ hot cell.In the post of this temperature, inject tetrahydrofuran as solvent with the flow velocity of per minute 1ml, and inject the GPC sample (10 μ l) of above-mentioned acquisition.As described post, use post TSKgel Super HM-M (making) by Tohso Corporation.

When measuring the weight-average molecular weight of resin to be measured, based on the molecular weight distribution that the logarithm value and the relation between the count number of calibration curve are calculated resin to be measured, described calibration curve is by using a plurality of monodisperse polystyrene sample makings.As the polystyrene standard sample that is used to make calibration curve, using molecular weight is 3,500,12,000,40,000,75,000,98,000,120,000,240,000,500,000,800,000 and 1, ten monodisperse polystyrene samples (making) altogether of 800,000 by Aldrich.As detecting device, use RI (refractive index) detecting device.

The copolymerization ratio of the aforementioned vibrin that will use can be passed through conventional method in the present invention, that is, measure the scaling method of the peak area ratio of the hydrogen atom (constituting the hydrogen atom of resin) that obtains based on the 1H-NMR by resin and confirm.

For example, can be by the synthetic above-mentioned vibrin that will use in the present invention of the ester-interchange method between dicarboxylic ester and the diol compound.Selectively, can be by the divalence acyl halide polyreaction synthesizing polyester resin between diacyl halogen (dicarboxylic acid halide) and the diol compound for example.

The synthesis example of the above-mentioned vibrin that will use will be described below in the present invention.

(synthesis example 1)

Have by above-mentioned formula (1-6), (1-12), (2-12) and (2-24) vibrin A1 synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (24.6g) of following formula (6-1) expression with by the diacyl halogen (24.6g) that following formula (6-2) is represented.

In addition, with described acyl halide solution dividually, will be dissolved in 10% sodium hydrate aqueous solution by the glycol with siloxane structure (21.7g) of following formula (7-1) expression with by the glycol (43.9g) of following formula (8-1) expression.In addition, add the tributyl benzyl ammonium chloride, with preparation diol compound solution as polymerization catalyst and stirring.

Then, above-mentioned acyl halide solution being added into above-mentioned diol compound solution stirs simultaneously with initiated polymerization.To state polymerization and under agitation carry out 3 hours, simultaneously temperature of reaction be maintained below 25 ℃.

Add acetate to stop polyreaction thereafter.Repeat to wash with water until with aqueous phase and.After washing, gained solution under agitation dropwise is added in the methyl alcohol with precipitation polymers.Described polymkeric substance is dry to obtain to have the vibrin A1 (80g) by above-mentioned formula (1-6), (1-12), (2-12) and the constitutional repeating unit (2-24) represented under vacuum.This is shown in Table 1.

Content as the siloxane position in vibrin A1 calculates as mentioned above, and it is 20 quality %.In addition, the weight-average molecular weight of vibrin A1 is 130,000.

(synthesis example 2 to 8)

Have by above-mentioned formula (1-6), (1-12), (2-12) and (2-24) vibrin A2-A8 synthetic of the constitutional repeating unit of expression

The diacyl halogen (6-1) that in synthesis example 1, uses when control is synthetic and (6-2) and diol compound (7-1) and consumption (8-1) to synthesize the vibrin A2-A8 shown in the table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin A2-A8 and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin A2-A8.Weight-average molecular weight is respectively:

Vibrin A2:120,000

Vibrin A3:100,000

Vibrin A4:80,000

Vibrin A5:130,000

Vibrin A6:150,000

Vibrin A7:120,000

Vibrin A8:100,000.

(synthesis example 9)

Have by above-mentioned formula (1-7), (1-13), (2-12) and (2-24) vibrin B1 synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (24.4g) of above-mentioned formula (6-1) expression with by the diacyl halogen (24.4g) that above-mentioned formula (6-2) is represented.

In addition; with described acyl halide solution dividually; use is by the glycol with siloxane structure (21.0g) of following formula (7-2) expression and the glycol of being represented by above-mentioned formula (8-1) (44.2g); carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin B 1 (70g) by above-mentioned formula (1-7), (1-13), (2-12) and the constitutional repeating unit (2-24) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate vibrin B 1 the siloxane position content and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin B 1.The weight-average molecular weight of vibrin B1 is 125,000.

(synthesis example 10 to 12)

Have by above-mentioned formula (1-7), (1-13), (2-12) and (2-24) vibrin B2-B4 synthetic of the constitutional repeating unit of expression

The diacyl halogen (6-1) that in synthesis example 9, uses when control is synthetic and (6-2) and diol compound (7-2) and consumption (8-1) to synthesize the vibrin B2-B4 shown in the table 1.

In addition, with synthesis example 1 in identical mode calculate vibrin B2-B4 the siloxane position content and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin B2-B4.Weight-average molecular weight is respectively:

Vibrin B2:130,000

Vibrin B3:90,000

Vibrin B4:140,000

(synthesis example 13)

Have by above-mentioned formula (1-8), (1-14), (2-9) and (2-21) vibrin C synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (24.9g) of above-mentioned formula (6-1) expression with by the diacyl halogen (24.9g) that above-mentioned formula (6-2) is represented.

In addition; with described acyl halide solution dividually; use is by the glycol with siloxane structure (21.8g) of following formula (7-3) expression and the glycol of being represented by following formula (8-2) (43.5g); carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin C (70g) by above-mentioned formula (1-8), (1-14), (2-9) and the constitutional repeating unit (2-21) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin C and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin C.Weight-average molecular weight is 120,000.

(synthesis example 14)

Have by above-mentioned formula (1-9), (1-15), (2-15) and (2-27) vibrin D synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (24.0g) of above-mentioned formula (6-1) expression with by the diacyl halogen (24.0g) that above-mentioned formula (6-2) is represented.

In addition; with described acyl halide solution dividually; use is by the glycol with siloxane structure (23.5g) of following formula (7-4) expression and the glycol of being represented by following formula (8-3) (44.5g); carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin D (70g) by above-mentioned formula (1-9), (1-15), (2-15) and the constitutional repeating unit (2-27) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin D and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin D.Weight-average molecular weight is 100,000.

(synthesis example 15)

Have by above-mentioned formula (1-10), (1-16), (2-7) and (2-19) vibrin E synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (28.0g) of above-mentioned formula (6-1) expression with by the diacyl halogen (28.0g) that above-mentioned formula (6-2) is represented.

In addition; with described acyl halide solution dividually; use is by the glycol with siloxane structure (21.3g) of following formula (7-5) expression and the glycol of being represented by following formula (8-4) (38.4g); carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin E (60g) by above-mentioned formula (1-10), (1-16), (2-7) and the constitutional repeating unit (2-19) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin E and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin E.Weight-average molecular weight is 150,000.

(synthesis example 16)

Have by above-mentioned formula (1-11), (1-17), (2-12) and (2-24) vibrin F synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (24.3g) of above-mentioned formula (6-1) expression with by the diacyl halogen (24.3g) that above-mentioned formula (6-2) is represented.

In addition; with described acyl halide solution dividually; use is by the glycol with siloxane structure (20.6g) of following formula (7-6) expression and the glycol of being represented by above-mentioned formula (8-1) (44.3g); carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin F (60g) by above-mentioned formula (1-11), (1-17), (2-12) and the constitutional repeating unit (2-24) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin F and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin F.Weight-average molecular weight is 140,000.

(synthesis example 17)

Have by above-mentioned formula (1-26), (1-27), (2-12) and (2-24) vibrin G synthetic of the constitutional repeating unit of expression

In addition; with described acyl halide solution dividually; use is by the glycol with siloxane structure (21.3g) of following formula (7-7) expression and the glycol of being represented by above-mentioned formula (8-1) (44.2g); carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin G (65g) by above-mentioned formula (1-26), (1-27), (2-12) and the constitutional repeating unit (2-24) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin G and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin G.Weight-average molecular weight is 120,000.

(synthesis example 18)

Have by the above-mentioned formula (1-21) and (2-33) vibrin H synthetic of the constitutional repeating unit of expression

To be dissolved in by the diacyl halogen (51.7g) of following formula (6-3) expression in the methylene chloride with preparation acyl halide solution.

In addition; with described acyl halide solution dividually; use have siloxane structure and by the glycol (21.7g) of above-mentioned formula (7-1) expression and by the glycol (40.6g) of following formula (8-5) expression carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin H (70g) by above-mentioned formula (1-21) and the constitutional repeating unit (2-33) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin H and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin H.Weight-average molecular weight is 120,000.

(synthesis example 19)

Have by the above-mentioned formula (1-22) and (2-33) vibrin I synthetic of the constitutional repeating unit of expression

To be dissolved in by the diacyl halogen (51.4g) of above-mentioned formula (6-3) expression in the methylene chloride with preparation acyl halide solution.

In addition; with described acyl halide solution dividually; use has siloxane structure and by the glycol (21.0g) of above-mentioned formula (7-2) expression with by the glycol (41.2g) of above-mentioned formula (8-5) expression; carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin I (65g) by above-mentioned formula (1-22) and the constitutional repeating unit (2-33) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin I and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin I.Weight-average molecular weight is 130,000.

(synthesis example 20)

Have by the above-mentioned formula (1-23) and (2-33) vibrin J synthetic of the constitutional repeating unit of expression

To be dissolved in by the diacyl halogen (52.7g) of above-mentioned formula (6-3) expression in the methylene chloride with preparation acyl halide solution.

In addition; with described acyl halide solution dividually; use has siloxane structure and by the glycol (23.5g) of above-mentioned formula (7-4) expression with by the glycol (40.2g) of above-mentioned formula (8-5) expression; carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin J (60g) by above-mentioned formula (1-23) and the constitutional repeating unit (2-33) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin J and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin J.Weight-average molecular weight is 110,000.

(synthesis example 21)

Have by the above-mentioned formula (1-24) and (2-33) vibrin K synthetic of the constitutional repeating unit of expression

To be dissolved in by the diacyl halogen (51.2g) of above-mentioned formula (6-3) expression in the methylene chloride with preparation acyl halide solution.

In addition; with described acyl halide solution dividually; use has siloxane structure and by the glycol (20.6g) of above-mentioned formula (7-6) expression with by the glycol (41.3g) of above-mentioned formula (8-5) expression; carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin K (60g) by above-mentioned formula (1-24) and the constitutional repeating unit (2-33) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin K and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin K.Weight-average molecular weight is 160,000.

(synthesis example 22)

Have by above-mentioned formula (1-21), (1-12), (2-34) and (2-24) vibrin L synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (34.6g) of above-mentioned formula (6-3) expression with by the diacyl halogen (15.4g) that above-mentioned formula (6-2) is represented.

In addition; with described acyl halide solution dividually; use has by the glycol (21.7g) of above-mentioned formula (7-1) expression and the glycol of being represented by above-mentioned formula (8-1) (42.7g); carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin L (65g) by above-mentioned formula (1-21), (1-12), (2-34) and the constitutional repeating unit (2-24) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin L and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin L.Weight-average molecular weight is 120,000.

(synthesis example 23)

Have by above-mentioned formula (1-22), (1-13), (2-34) and (2-24) vibrin M synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (34.3g) of above-mentioned formula (6-3) expression with by the diacyl halogen (15.1g) that above-mentioned formula (6-2) is represented.

In addition; with described acyl halide solution dividually; use has siloxane structure and by the glycol (21.0g) of above-mentioned formula (7-2) expression with by the glycol (43.0g) of above-mentioned formula (8-1) expression; carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin M (60g) by above-mentioned formula (1-22), (1-13), (2-34) and the constitutional repeating unit (2-24) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin M and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin M.Weight-average molecular weight is 125,000.

(synthesis example 24)

Have by above-mentioned formula (1-23), (1-15), (2-34) and (2-24) vibrin N synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (35.4g) of above-mentioned formula (6-3) expression with by the diacyl halogen (15.5g) that above-mentioned formula (6-2) is represented.

In addition; with described acyl halide solution dividually; use has siloxane structure and by the glycol (23.5g) of above-mentioned formula (7-4) expression with by the glycol (42.0g) of above-mentioned formula (8-1) expression; carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin N (60g) by above-mentioned formula (1-23), (1-15), (2-34) and the constitutional repeating unit (2-24) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin N and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin N.Weight-average molecular weight is 95,000.

(synthesis example 25)

Have by above-mentioned formula (1-24), (1-17), (2-34) and (2-24) vibrin O synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (34.2g) of above-mentioned formula (6-3) expression with by the diacyl halogen (15.1g) that above-mentioned formula (6-2) is represented.

In addition; with described acyl halide solution dividually; use has siloxane structure and by the glycol (20.6g) of above-mentioned formula (7-6) expression with by the glycol (34.2g) of above-mentioned formula (8-1) expression; carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin O (60g) by above-mentioned formula (1-24), (1-17), (2-34) and the constitutional repeating unit (2-24) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin O and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin O.Weight-average molecular weight is 155,000.

(synthesis example 26)

Have by the above-mentioned formula (1-1) and (2-1) vibrin P synthetic of the constitutional repeating unit of expression

To be dissolved in by the diacyl halogen (40.6g) of following formula (6-4) expression in the methylene chloride with preparation acyl halide solution.

In addition; with described acyl halide solution dividually; use has siloxane structure and by the glycol (21.7g) of above-mentioned formula (7-1) expression with by the glycol (55.4g) of above-mentioned formula (8-1) expression; carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin P (65g) by above-mentioned formula (1-1) and the constitutional repeating unit (2-1) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin P and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin P.Weight-average molecular weight is 105,000.

(synthesis example 27)

Have by the above-mentioned formula (1-2) and (2-2) vibrin Q synthetic of the constitutional repeating unit of expression

To be dissolved in by the diacyl halogen (42.7g) of following formula (6-5) expression in the methylene chloride with preparation acyl halide solution.

In addition; with described acyl halide solution dividually; use has siloxane structure and by the glycol (21.7g) of above-mentioned formula (7-1) expression with by the glycol (52.0g) of above-mentioned formula (8-1) expression; carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin Q (60g) by above-mentioned formula (1-2) and the constitutional repeating unit (2-2) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin Q and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin Q.Weight-average molecular weight is 140,000.

(synthesis example 28)

Have by above-mentioned formula (1-1), (1-12), (2-1) and (2-24) vibrin R synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (16.0g) of above-mentioned formula (6-4) expression with by the diacyl halogen (31.5g) that above-mentioned formula (6-2) is represented.

In addition; with described acyl halide solution dividually; use has siloxane structure and by the glycol (21.7g) of above-mentioned formula (7-1) expression with by the glycol (47.2g) of above-mentioned formula (8-1) expression; carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin R (65g) by above-mentioned formula (1-1), (1-12), (2-1) and the constitutional repeating unit (2-24) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin R and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin R.Weight-average molecular weight is 120,000.

(synthesis example 29)

Have by above-mentioned formula (1-2), (1-12), (2-2) and (2-24) vibrin S synthetic of the constitutional repeating unit of expression

To be dissolved in the methylene chloride with preparation acyl halide solution by the diacyl halogen (15.2g) of above-mentioned formula (6-5) expression with by the diacyl halogen (32.4g) that above-mentioned formula (6-2) is represented.

In addition; with described acyl halide solution dividually; use has siloxane structure and by the glycol (21.7g) of above-mentioned formula (7-1) expression with by the glycol (46.3g) of above-mentioned formula (8-1) expression; carry out with synthesis example 1 in identical operations, thereby obtain to have vibrin S (60g) by above-mentioned formula (1-2), (1-12), (2-2) and the constitutional repeating unit (2-24) represented.This is shown in Table 1.

In addition, with synthesis example 1 in identical mode calculate the content at siloxane position in vibrin S and be shown in Table 1.

In addition, with synthesis example 1 in identical mode measure the weight-average molecular weight of vibrin S.Weight-average molecular weight is 130,000.

Table 1

As the charge transport layer of electrophotographic photosensitive element superficial layer of the present invention comprise have by the constitutional repeating unit of above-mentioned formula (1) expression and by the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression as resin glue.Can blend and other resin that comes into operation.

The example of resin glue that can blend comprises acrylic resin, styrene resin, vibrin, polycarbonate resin, polysulfone resin, polyphenylene oxide resin, epoxy resin, urethane resin, alkyd resin and unsaturated polyester.In these, preferred polyester resin or polycarbonate resin.These can use separately or with one or more potpourris or multipolymer.

When being used in combination other vibrin, can use the vibrin that has by the constitutional repeating unit of above-mentioned formula (2) expression.In them, the vibrin with constitutional repeating unit of being represented by above-mentioned formula (2-1)-(2-40) is preferred.In addition, have by above-mentioned formula (2-1), (2-2), (2-8), (2-9), (2-10), (2-12), (2-17), (2-20), (2-21), (2-22), (2-24), (2-29), (2-33), (2-34) or (2-35) vibrin of the constitutional repeating unit of expression be preferred.

The instantiation of the constitutional repeating unit of the polycarbonate resin that can be used in combination is shown in following.

In these, by above-mentioned formula (9-1), (9-4) and (9-6) constitutional repeating unit of expression be preferred.

In the present invention, be not less than 60 quality % owing to have with respect to the gross mass of whole resin glues of the charge transport layer that constitutes electrophotographic photosensitive element, so can obtain to relax the effect of contact stress by the constitutional repeating unit of above-mentioned formula (1) expression with by the content of the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression.

In addition, in order to satisfy the potential stability during relaxing contact stress and reusing evenly, preferably in the charge transport layer of electrophotographic photosensitive element, have to be preferably with respect to the gross mass of whole resin glues of charge transport layer and be not less than 5 quality % to being not more than 30 quality % and more preferably being not less than 10 quality % to being not more than 25 quality % by the constitutional repeating unit of above-mentioned formula (1) expression with by the content at the siloxane position in the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression.

As the charge transport material that in being used as the charge transport layer of electrophotographic photosensitive element superficial layer of the present invention, comprises, for example, can mention triarylamine compounds, hydrazone compound, compound of styryl, stilbene compounds, pyrazoline compounds, oxazole compound, thiazolium compounds and triaryl methane compounds.These charge transport materials can use separately or with two or more potpourris.In addition, in these,, preferably triarylamine compounds is used as the charge transport material in order to improve the electrofax characteristic.In addition, in triarylamine compounds, the preferred compound that uses by following formula (4) expression:

＜in formula (4), Ar ¹To Ar ⁴Expression independently of one another replaces or unsubstituted aryl; And Ar ⁵And Ar ⁶Expression independently of one another replaces or unsubstituted arlydene 〉.

In above-mentioned formula (4), Ar ¹To Ar ⁴Expression independently of one another replaces or unsubstituted aryl.As aryl, for example, can mention phenyl and naphthyl.In these, phenyl is preferred.The substituting group that can have as aryl for example, can be mentioned alkyl, aryl, alkoxy and have the monoradical of unsaturated link.

In above-mentioned formula (4), Ar ⁵And Ar ⁶Expression independently of one another replaces or unsubstituted arlydene.As arlydene, for example, can mention phenylene and naphthylene.In these, phenylene is preferred.

Examples for compounds by above-mentioned formula (4) expression is shown in following.

In these, be preferred (4-1) or (4-7).

Since as the charge transport layer of electrophotographic photosensitive element superficial layer of the present invention with predetermined content comprise have by the constitutional repeating unit of above-mentioned formula (1) expression and by the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression as resin glue, therefore can obtain the lasting mitigation and the gratifying electrofax characteristic of contact stress with balancing each other.

Compound by above-mentioned formula (4) expression advantageously has high charge delivery capability; Yet compatibility becomes the problem of the composition that depends on the resin glue that constitutes charge transport layer sometimes.Especially, the conventional resin that contains the silica alkyl structure in use is with under the situation that relaxes contact stress, because the compatibility between siloxane position and the charge transport material is tending towards low, in the resin that contains the silica alkyl structure, the charge transport material aggregation, electrofax characteristic as a result sometimes worsens.

Owing to comprise with predetermined content as the charge transport layer of electrophotographic photosensitive element superficial layer of the present invention and to have by the constitutional repeating unit of above-mentioned formula (1) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression, described vibrin is to contain a kind of in the resin of silica alkyl structure, therefore, also can obtain to relax the effect of stress and do not destroy the electrofax characteristic even will be by the compound of above-mentioned formula (4) expression as the charge transport material.

In addition, on surface, can form concaveconvex shape (unevenness profile) (depression and projection) as the charge transport layer of the superficial layer of electrophotographic photosensitive element of the present invention.Depend on the formation of concaveconvex shape, can improve the effect that relaxes contact stress.Concaveconvex shape can form by known method.Its instantiation can comprise: the method that the organic or inorganic particle is added into superficial layer, abrasive grains is sprayed on the superficial layer surface of electrophotographic photosensitive element on the surface of superficial layer, to form the method for depression, on making mould under the situation of exerting pressure and the surface of electrophotographic photosensitive element superficial layer contacts with the surface at superficial layer, form the method for concaveconvex shape with concaveconvex shape, forming on the film surface that forms by the superficial layer coating fluid that drop and dry this drop form the method for depression on the surface at superficial layer and forming the method that caves in by the surface that laser light is applied to the electrophotographic photosensitive element superficial layer in the surface at superficial layer by dewfall.In these, the method that forms concaveconvex shape on making mould with concaveconvex shape under the situation of exerting pressure and the surface of electrophotographic photosensitive element superficial layer contacts with the surface at superficial layer is preferred.In addition, forming drop and dry drop by dewfall on the film surface that is formed by the superficial layer coating fluid is preferred to form the method that caves in.

With being described in the mould with concaveconvex shape is contacted to form the method for concaveconvex shape on the surface of superficial layer with the surface of the superficial layer of electrophotographic photosensitive element.

In that the mould with concaveconvex shape is contacted with the surface of the superficial layer of electrophotographic photosensitive element with the method that forms concaveconvex shape is to make the mould with reservation shape contact method with the transfer printing shape with the surface of the superficial layer of electrophotographic photosensitive element under the situation of exerting pressure.

Fig. 1 is the figure that schematically illustrates the crimping shape transferred thereon/process equipment that utilizes mould.

Predetermined mold B is mounted to the pressurized equipment A that can repeat to pressurize with release., apply described mould with the cylindric supporting mass C that have thereon the superficial layer that form contacted thereafter, thus the transfer printing shape., once unload applied pressure, and make cylindric supporting mass C rotation, then, exert pressure once more with the transfer printing shape thereafter.By repeating this step, can on the electrophotographic photosensitive element whole circumference, form reservation shape.

In addition, for example, as shown in Figure 2, the mould B that will have the reservation shape corresponding with the full girth on the superficial layer surface of cylindric supporting mass C is mounted to pressurized equipment A.When predetermined pressure being applied to cylindric supporting mass C, making direction rotation that cylindric supporting mass C follow the arrow and move thereafter.In this way, on the whole circumference of electronics Electrifier frame, photoreceptor, form predetermined concaveconvex shape.

In addition, can with the sheet mould holding between roll forming pressurized equipment and cylindric supporting mass C and the feeding die blade to carry out surface working.

In addition, for transfer printing shape effectively, but heating mould and cylindric supporting mass C.The heating-up temperature of described mould and cylindric supporting mass C can at random be provided with, as long as can form reservation shape; Yet,, preferably temperature is set at low as far as possible in order stably to form shape.

Can suitably select material, the size and dimension of mould itself.As the mould material, can mention metal, the surface that handle with microfabrication on its surface utilize the resist patterning silicon wafer, have the fine grained of dispersion or have predetermined fine surface configuration and with the resin molding of metal coating.

In addition, in order to exert pressure equably, can between mould and pressurized equipment, elastic component be set to electrophotographic photosensitive element.

Next, below will describe and on the film surface that forms by the superficial layer coating fluid, form drop and dry drop by dewfall and forms the method that caves in surface at electrophotographic photosensitive element.

As the method that is used on the film surface that forms by the superficial layer coating fluid, forming drop by dewfall, can mention the supporting mass with the coating of superficial layer coating fluid is kept the schedule time method of (wherein drop can be formed on the film coated surface by dewfall) and will have the organic compound of high-affinity to be added into the method for superficial layer coating fluid to glassware for drinking water under atmosphere.

Dewfall in surface formation method is meant that the effect by water forms drop on film coated surface.Be used for being subjected to being used to keeping the relative humidity of atmosphere of supporting mass and solvent evaporation conditions (for example, the heat of evaporation) influence of coating fluid by dewfall forms drop on filming condition.Therefore, importantly select suitable condition.Especially, described condition depends primarily on the relative humidity that keeps supporting mass atmosphere.By dewfall the relative humidity that forms drop on the film coated surface be preferably 40% or more to below 100% with more preferably more than 60% to below 95%.To carry out random time by dewfall forms drop on film coated surface step, as long as form drop by dewfall.From productive angle, this time is preferably more than 1 second to below 300 seconds, more preferably more than 10 seconds to below 180 seconds.In the step that droplet-shaped is formed on the film coated surface, relative humidity is important; Yet atmosphere temperature is preferably more than 20 ℃ to below 80 ℃.

In addition, be suitable in film coated surface, forming the superficial layer coating fluid of the method for concaveconvex shape, can mention the solution that contains aromatic organic solvent.Described aromatic organic solvent is preferred, and this is because it is that glassware for drinking water is had the solvent of low compatibility and stably form shape in the dewfall step.Particularly, can mention 1,2-dimethyl benzene, 1,3-dimethyl benzene, 1,4-dimethyl benzene, 1,3,5-trimethylbenzene and chlorobenzene.In addition, aromatic organic solvent is preferably with respect to the content of whole solvents of superficial layer coating fluid and is not less than 50 quality % to being not more than 80 quality %.

In addition, aromatic organic solvent is contained in the superficial layer coating fluid, can will have the organic compound of high-affinity to be added into the superficial layer coating fluid to glassware for drinking water in addition.As the organic compound that glassware for drinking water is had high-affinity, can mention the organic solvent that glassware for drinking water is had high-affinity.Compatibility to water can be measured by the following method.

＜to the evaluation of the compatibility of water 〉

Normal temperature/normal wet environment (25 ℃, relative humidity: 55%), at first, measure water (50ml) by the 50ml graduated cylinder.Then, measure the solvent (50ml) that will use by the 100ml graduated cylinder.To wherein, add the water (50ml) of measuring and stir until making the complete soln homogenising by glass bar by aforementioned operation.Lid be set not make solvent and water evaporate, and make its sufficient standing until bubble and interface become stable thereafter.Observe the state of in 100ml graduated cylinder solution mixture and the volume of measurement water thereafter.If it is above to 5ml that the volume of water is 0ml, this solvent can be defined as hydrophilic solvent.

As the organic solvent of high-affinity being arranged with glassware for drinking water, for example, can mention 1, the 2-propylene glycol, 1, the 3-butylene glycol, 1, the 5-pentanediol, glycerine, 1,2, the 6-hexanetriol, tetrahydrofuran, diethylene glycol dimethyl ether, propionic acid, butyric acid, gamma-butyrolacton, the diglycol monotertiary acetic acid esters, monoacetin, diacetin, ethylene carbonate, propylene carbonate, triethyl phosphate, beta-picoline, γ-picoline, 2, the 4-lutidines, 2, the 6-lutidines, quinoline, formamide, N, dinethylformamide, N, the N-diethylformamide, N, the N-dimethyl acetamide, N, N, N ', N '-tetramethylurea, 2-Pyrrolidone, dimethyl sulfoxide (DMSO), sulfolane, cellosolvo, tetrahydrofurfuryl alcohol, diglycol, triethylene glycol, tetraethylene glycol, 1-ethoxy-2-propyl alcohol, dipropylene glycol, DPGME, dihydroxypropane single-ethyl ether, the tripropylene glycol monomethyl ether, diacetone alcohol, 3-chloro-1, the 2-propylene glycol, N butyl diethanol amine, triethanolamine, 2-methoxy ethyl acetic acid esters, diethylene glycol monoethyl ether acetate, hexamethyl phosphoric triamide, 1,3-dimethyl-2-imidazolone and N, N, N ', N '-tetramethylethylenediamine.In these, dimethyl sulfoxide (DMSO), sulfolane, triethylene glycol and dipropylene glycol are preferred.Can contain separately or contain these organic solvents with two or more combinations.

In addition, below be preferred: as character, the organic compound that necessarily requires glassware for drinking water is had a high-affinity not only has compatibility to the glassware for drinking water that produces by dewfall but also has compatibility for having by the constitutional repeating unit of above-mentioned formula (1) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression.This type of organic compound with above-mentioned character for example can be mentioned surfactant.As surfactant, for example, can mention anionic surfactant, cationic surfactant, non-ionic surfactant and amphoteric surfactant.As anionic surfactant, for example, can mention alkyl benzene sulfonate, alpha-alkene sulfonate or phosphate.As cationic surfactant, for example, can mention amine salt type surfactant or quaternary cationics.As amine salt type surfactant, for example, can mention alkylamine salt, amino alcohol fatty acid derivatives, polyamines derivative of fatty acid or imidazoline.As quaternary cationics, for example, can mention alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, pyridiniujm, alkyl isoquinolinium salt or benzethonium chloride.As non-ionic surfactant, for example, can mention aliphatic amide derivatives or polyol derivative.As amphoteric surfactant, for example, can mention alanine, dodecyl two (amino-ethyl) glycocoll, two (octyl group amino-ethyl) glycocoll or N-alkyl-N, N-Dimethyl Ammonium betaine (N-alkyl-N, N-dimethyl ammoniumbetain).In these, because non-ionic surfactant has gratifying electrofax characteristic, so it is preferred.In addition, polyvalent alcohol is preferred.Examples of polyhydric alcohols comprises high molecular weight alkyl alcohol for example triethylene glycol, tetraethylene glycol, polyglycol, dipropylene glycol and three (dipropylene glycol); High molecular weight fatty acid ester is sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid ester, fatty acid glyceride, ten fatty acid glycerides (decaglycerinfatty acid ester), polyglyceryl fatty acid ester and cithrol for example; High molecular weight alkyl ether is polyethylene oxide alkyl ethers and polyethylene oxide alkyl phenyl ether for example; High molecular weight alkyl amine is the polyethylene oxide alkyl amine for example; The high molecular weight fatty acid acid amides is polyethylene oxide alkyl fatty acid acid amides for example; High molecular weight fatty acid salt is the polyethylene oxide alkyl ethers acetate for example; With high molecular weight alkyl ether phosphate polyethylene oxide alkyl ethers phosphate for example.

These have in the organic compound of high-affinity glassware for drinking water, and having the hydrophilic lipophilic balance of calculating by Davis's method (Davis method) (HLB value) is preferred for the organic compound of 6-12.

By dewfall after forming drop on the film coated surface by the superficial layer coating fluid, desciccator diaphragm.In its dehydration,, can mention heat drying, forced air drying and vacuum drying as dewatering.In addition, can be used in combination these dewaterings.Especially, from productive angle, heat drying and heating/forced air drying are preferred.In addition, for the height adequate relief is in depression, fast dewatering is crucial.For this, heat drying is preferred.Dehydration temperaturre is preferably more than 100 ℃ to below 150 ℃.As the time of dehydration, can adopt any time, as long as remove solvent that comprises in the coating fluid that on matrix, applies and the drop that in the dewfall step, forms.The time of dehydration be preferably more than 20 minutes to below 120 minutes and further preferred more than 40 minutes to below 100 minutes.

In the shape by dewfall forms, can control shape by control generation condition.Type that can be by changing the solvent comprise in the superficial layer coating fluid, solvent, the relative humidity in the dewfall step, retention time and the dehydration temperaturre in the dewfall step are controlled depression.

Can on the electrophotographic photosensitive element surface, form a plurality of depressions and projection by the aforementioned concave-convex surface shape formation method that is used for electrophotographic photosensitive element.

As the concave shape that forms on electrophotographic photosensitive element surface, viewed as the vertical view of electrophotographic photosensitive element, can mention the shape that is formed by straight lines, the shape that forms by curve and the shape that forms by straight line and curve.As the shape that is formed by straight lines, for example, for example, can mention triangle, quadrangle, pentagon and sexangle.As the shape that forms by curve, for example, can mention circle and ellipse.As the shape that forms by straight line and curve, for example, can mention quadrangle, the sexangle with fillet and fan-shaped with fillet.

In addition, as the concave shape that in the electrophotographic photosensitive element surface, forms,, can mention the shape that is formed by straight lines as the sectional view of electrophotographic photosensitive element, the shape that forms by curve and the shape that forms by straight line and curve.As the shape that is formed by straight lines, for example, can mention triangle, quadrangle and pentagon.As the shape that forms by curve, for example, can mention that part circular and part are oval.As the shape that forms by straight line and curve, for example, can mention quadrangle with fillet and fan-shaped.The shape of the depression that forms in the electrophotographic photosensitive element surface, size and the degree of depth can differ from one another.Selectively, all depressions can be of similar shape, size and the degree of depth.In addition, the electrophotographic photosensitive element surface of manufacturing can have the depression of difformity, size and the degree of depth and have identical shaped, size and the combination of the depression of the degree of depth.In addition, these shapes can have overlapping part or pile up each other mutually.

The size of the concave shape that forms on the electrophotographic photosensitive element surface will be described in.

As the index of depressed part shape, use major axis footpath size.Major axis footpath size is meant the maximum length in the straight line that passes each depressed part peristome; In other words, be meant that the outer peripheral face with depression peristome in the surface of electrophotographic photosensitive element is a benchmark, the maximum length of the surface opening portion of each depression.More specifically, when the surface configuration of depression is circle, be meant diameter of a circle.When surface configuration is ellipse, be meant its major diameter.When shape is quadrangle, be meant the diagonal line that it is long.Directly to be preferably 0.5 μ m above to 80 μ m for the major axis of concave shape in the electrophotographic photosensitive element surface, and in addition, preferred 1 μ m is above to 40 μ m, and further below the preferred 20 μ m.

The degree of depth of the depression that forms on the electrophotographic photosensitive element surface will be described in.

As the index of above-mentioned depression, use the degree of depth.The described degree of depth is meant the deep of each depression and the distance between the open surfaces, more specifically, is meant that the outer peripheral face with the lip-deep recessed openings of electrophotographic photosensitive element portion is a benchmark, the deep of depression and the distance between the open surfaces.In the electrophotographic photosensitive element surface, it is above to 10 μ m that the degree of depth of depression is preferably 0.1 μ m, and more preferably 0.3 μ m is above to 7 μ m and further below the preferred 5 μ m.

Wherein form the zone in the electrophotographic photosensitive element surface of caving in, can be all or part of for it; Yet depression preferably forms in all surfaces zone.

In addition, in the lip-deep depression of electrophotographic photosensitive element preferably with per unit area (10000 μ m ²(100 μ m are square)) in be to be present on the electrophotographic photosensitive element surface to the ratio below 70,000 more than 1, and more preferably more than 100 to below 50,000.

As the convex shape that on the electrophotographic photosensitive element surface, forms, as the vertical view of electrophotographic photosensitive element, can mention the shape that is formed by straight lines, the shape that forms by curve and the shape that forms by straight line and curve.As the shape that is formed by straight lines, for example, can mention triangle, quadrangle, pentagon and sexangle.As the shape that forms by curve, for example, can mention circle and ellipse.As the shape that forms by straight line and curve, for example, can mention quadrangle, the sexangle with fillet and fan-shaped with fillet

In addition, as the convex shape that on the electrophotographic photosensitive element surface, forms,, can mention the shape that is formed by straight lines as the sectional view of electrophotographic photosensitive element, the shape that forms by curve and the shape that forms by straight line and curve.As the shape that is formed by straight lines, for example, can mention triangle, quadrangle and pentagon.As the shape that forms by curve, for example, can mention that part circular and part are oval.As the shape that forms by straight line and curve, for example, can mention quadrangle with fillet and fan-shaped.

The shape of the convex shape that forms on the electrophotographic photosensitive element surface, size and height can differ from one another.Selectively, all projectioies can be of similar shape, size and the height.In addition, these shapes can have overlapping or pile up each other mutually.

The size of the projection that forms on the electrophotographic photosensitive element surface will be described in.

As the index of projection, use major axis footpath size.Major axis footpath size is meant that the outer peripheral face with each lug boss is a benchmark, the maximum length of the part that each projection contacts with described outer peripheral face.For example, when raised surface is shaped as circle, be meant diameter of a circle.When surface configuration is ellipse, be meant its major diameter.When shape is quadrangle, be meant the longest diagonal line.It is above to 40 μ m that the major axis of the projection on electrophotographic photosensitive element surface directly is preferably 0.5 μ m, and in addition, preferred 1 μ m is above to 20 μ m and further below the preferred 10 μ m.

The height of the convex shape that forms on the electrophotographic photosensitive element surface will be described in.

As the index of above-mentioned projection, use height.This highly is meant top that each is protruding and the distance between the outer peripheral face.Be preferably more than the 0.1 μ m to 10 μ m at the height of the lip-deep projection of electrophotographic photosensitive element, in addition, preferred 0.3 μ m is above to 7 μ m and further below the preferred 5 μ m.

The zone that wherein forms the electrophotographic photosensitive element surface of projection can be all or part of electrophotographic photosensitive element surface; Yet projection preferably forms in all surfaces zone.In addition, in the lip-deep projection of electrophotographic photosensitive element preferably with per unit area (10000 μ m ²(100 μ m are square)) in be to be present in the electrophotographic photosensitive element surface to the ratio below 70,000 more than 1, and more preferably more than 100 to below 50,000.

The lip-deep concaveconvex shape of electrophotographic photosensitive element can be by for example laser microscope, optical microscope, electron microscope or the atomic force microscope measurement of microscope that is obtained commercially.

As laser microscope, for example, can use instrument as super depth profile measuring microscope VK-8550 (making), super depth profile measuring microscope VK-9000 (making) and super depth profile measuring microscope VK-9500 (by Keyence Corporation manufacturing), the Surface Explorer SX-520DR of surface profile measurement system type instrument (by Ryoka Systems Inc. manufacturing) by Keyence Corporation by Keyence Corporation; Sweep type confocal laser microscope OLS3000 (making) and true color (real color) Laser Scanning Confocal Microscope Optics C130 (making) by LasertecCorporation by Olympus Corporation.

As optical microscope, for example, can use instrument for example digital microscope VHX-500 (making), digital microscope VHX-200 (making) and 3D digital microscope VC-7700 (making) by Omron Corporation by Keyence Corporation by Keyence Corporation.

As electron microscope, for example, can use instrument for example to comprise the true surface observation of 3D (real surface-view) microscope VE-9800 (making), the true surface observation microscope of 3D VE-8800 (making), scanning electron microscope routine/variable pressure SEM (making), scanning electron microscope SUPERS CAN SS-550 (making) by ShimadzuCorporation by SII NanoTechnologyInc. by Keyence Corporation by Keyence Corporation.

As atomic force microscope, for example, can use instrument for example nanoscale mixing microscope VN-8000 (making), scanning probe microscopy NanoNavi station (making) and scanning probe microscopy SPM-9600 (making) by Shimadzu Corporation by SII NanoTechnology Inc. by Keyence Corporation.

Use aforesaid microscope, can under predetermined enlargement ratio, measure depressed part and protruding major axis footpath, the degree of depth and height in the visual field (will measure).

As an example, description is utilized routine analyzer pass through the measurement of Surface ExplorerSX-520DR type instrument.

The electrophotographic photosensitive element that will measure is placed on the worktable and regulates the inclined-plane so that the worktable level.Be written into the three-dimensional shape data on electrophotographic photosensitive element surface with network schemer (web mode).At this moment, the enlargement ratio of object lens can be arranged on 50 times, and at 100 μ m * 100 μ m (10,000 μ m ²) observe in the visual field.

Then, use the grain size analysis program in the data analysis software, show the contour line data on electrophotographic photosensitive element surface.

Shape, the major axis footpath of the analytical parameters of concaveconvex shape such as depressed part and projection, the degree of depth and highly all can optimize according to the concaveconvex shape that forms.For example, when observing and measuring major axis and directly be the concaveconvex shape of about 10 μ m, the major axis upper limit directly can be set in 15 μ m; The lower limit set in major axis footpath is at 1 μ m; Degree of depth lower limit set is at 0.1 μ m; With the volume lower limit set at 1 μ m ³More than.In addition, be defined as the concaveconvex shape of depressed part and projection and be defined as the quantity of concaveconvex shape on the analysis of accounts screen.

Notice that the concaveconvex shape with the following major axis of about 1 μ m footpath can be by laser microscope and observation by light microscope.Yet in order to improve measuring accuracy, expectation is used in combination observation and the measurement by electron microscope.

Now, will the structure of electrophotographic photosensitive element of the present invention be described.

As mentioned above, electrophotographic photosensitive element of the present invention is to have supporting mass, be arranged at the charge generation layer on the described supporting mass and be arranged at the electrophotographic photosensitive element of the charge transport layer on the charge generation layer, and also be wherein charge transport layer as the electrophotographic photosensitive element of the superficial layer (the superiors) of electrophotographic photosensitive element.

In addition, the charge transport layer of electrophotographic photosensitive element of the present invention comprises charge transport material and resin glue.In addition, charge transport layer comprise have by the constitutional repeating unit of above-mentioned formula (1) expression and by the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression as resin glue.

In addition, charge transport layer can be laminar structure.In this case, will have by the constitutional repeating unit of above-mentioned formula (1) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression and introduce at least in the charge transport layer on outmost surface layer side.As electrophotographic photosensitive element, be extensive use of the cylindric electrophotographic photosensitive element that has the photographic layer that on cylindric supporting mass, forms usually; Yet the electrophotographic photosensitive element that can use other shape is the electrophotographic photosensitive element of band shape or sheet for example.

As described supporting mass, preferably have the supporting mass (electric conductivity supporting mass) of electric conductivity, also can use the supporting mass that forms by metal such as aluminium, aluminium alloy and stainless steel.

Under the situation of the supporting mass that forms by aluminum or aluminum alloy, can use ED pipe, EI pipe and cutting or utilize these pipes of electrolysis multiple grinding (electropolishing) (grinding of electrolysis that electrode by having electrolytic action and electrolyte solution carry out and the grinding stone by having abrasive action) and wet method or dry sanding processing.

In addition, can use metal support or have the resin support body of the rete that forms by vacuum deposited aluminum, aluminium alloy or indium oxide-tin oxide alloy.

As the resin support body, for example, can mention the supporting mass that forms by polyethylene terephthalate, polybutylene terephthalate, phenolics, polypropylene and polystyrene resin.

In addition, can use by the supporting mass of using the formation of conductive particle such as carbon black, granules of stannic oxide, titan oxide particles and silver-colored impregnated with particles resin or paper and plastics with conductive adhesive resin.

In order to prevent by light forming of the interference fringe that causes of laser scattering of light for example, the supporting mass surface can be applied with cutting handle, surface roughening is handled or pellumina is handled.

When being provided with on the supporting mass surface in order to give electric conductivity layer, the specific insulation of this layer is preferably 1 * 10 ¹⁰Below the Ω cm and especially more preferably 1 * 10 ⁶Below the Ω cm.

For preventing, between supporting mass and middle layer (narrating after a while) or charge generation layer, conductive layer can be set by the light interference fringe that causes of laser scattering of light or for covering the scratch of supporting mass for example.The layer that it forms for the conductive layer coating fluid that has the conductive particle that disperses by use in resin glue.

As conductive particle, for example, can mention carbon black, acetylene black, metal powder such as aluminium, nickel, iron, nickel-chrome, copper, zinc and silver; With metal oxide powder such as conductive tin oxide and ITO.

In addition, as resin glue, for example, can mention polystyrene, styrene-acrylonitrile copolymer, Styrene-Butadiene, styrene-maleic anhydride copolymer, polyester, Polyvinylchloride, vinyl chloride vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, the polyarylate resin, phenoxy resin, polycarbonate, the cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, the poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenolics and alkyd resin.

As the solvent that is used for the conductive layer coating fluid, for example, can mention ether solvent such as tetrahydrofuran and glycol dimethyl ether; Alcohols solvent such as methyl alcohol; Ketones solvent such as MEK; With aromatic hydrocarbon solvent such as toluene.

It is above to 40 μ m that the film thickness of conductive layer is preferably 0.2 μ m, and more preferably 1 μ m is above to 35 μ m, and further more preferably 5 μ m are above to 30 μ m.

Have the conductive particle of dispersion therein and the conductive layer of resistance control particle and be tending towards having roughened surface.

Middle layer with barrier functionality and attachment function can be set between supporting mass or conductive layer and charge generation layer.For example, in order to improve with the cohesive of photographic layer, improve the coating processability, to improve electric charge by supporting mass and inject and prevent that photographic layer is subjected to electrical damage, form the middle layer.

Described middle layer can be applied on the conductive layer by the middle layer coating fluid that will contain resin glue and its drying or sclerosis are formed.

Resin glue as the middle layer, for example, can mention water soluble resin such as polyvinyl alcohol (PVA), polyvinyl methyl ether, polyacrylic acid, methylcellulose, ethyl cellulose, polyglutamic acid or casein, polyamide, polyimide resin, polyamide-imide resin, polyamic acid resin, melamine resin, epoxy resin, urethane resin and polyglutamic acid esters resin.

For effectively developing the power block in middle layer, in addition, also in order to optimize coating, cohesive, solvent resistance and resistance, the resin glue in middle layer is preferably thermoplastic resin.More specifically, the thermoplastic polyamide resin is preferred.As described polyamide, the low crystallization or the amorphous nylon multipolymer that can apply with solution state are preferred.

The film thickness in middle layer be preferably 0.05 μ m above to 7 μ m and more preferably more than the 0.1 μ m to 2 μ m.

In addition, in order to prevent electric charge in the middle layer (charge carrier) flow disruption, conductive particle or electron transport material (electronics is accepted material such as acceptor) can be contained in the middle layer.

On supporting mass, conductive layer or middle layer, charge generation layer is set.

As the charge generation material that will be used for electrophotographic photosensitive element of the present invention, for example, can mention AZO pigments such as monoazo, bisdiazo and trisazo-; Phthalocyanine such as metal phthalocyanine, nonmetal phthalocyanine; Indigo pigment such as indigo and thioindigo; Perylene dye such as perylene acid anhydrides are with perylene acid acid imide; Many ring quinone pigments such as anthraquinone and pyrene quinone; Spiny dogfish (squarilium) coloring material, pyralium salt and thiapyran salt, triphenylmethane coloring material, dead matter such as selenium, selenium-tellurium and amorphous silicon; Quinacridone pigment, azulenes pigment salt, cyanine dye, xanthene coloring material, quinone imines coloring material and styryl coloring material.These charge generation materials can use separately or use as two or more potpourris.In these, special preferable alloy phthalocyanine such as titanium dioxide phthalocyanine, hydroxy gallium phthalocyanine and gallium chloride phthalocyanine, this is because it has ISO.

As the resin glue that uses in the charge generation layer, for example, can mention polycarbonate resin, vibrin, polyarylate resin, butyral resin, polystyrene resin, polyvinyl acetal resin, diallyl phthalate resin, acrylic resin, methacrylic resin, vinyl acetate resin, phenolics, silicone resin, polysulfone resin, Styrene-Butadiene resin, alkyd resin, epoxy resin, Lauxite and vinyl chloride vinyl acetate copolymer resin.In these, especially, preferred butyral resin.Can be separately or use these as two or more potpourri or multipolymer.

Can be by applying by with the charge generation material with resin glue is scattered in the charge generation layer coating fluid that obtains in the solvent and make its drying form charge generation layer.In addition, charge generation layer can be the deposited film of charge generation material.

As process for dispersing, for example, can mention the method for using homogenizer, ultrasound wave, bowl mill, sand mill, attitor and roller mill.

The ratio of charge generation material and resin glue preferably drops in the scope of 1: 10 to 10: 1 (mass ratio), especially more preferably in the scope of 1: 1 to 3: 1 (mass ratio)

The solvent that is used for the charge generation layer coating fluid can be selected based on the dissolubility and the dispersion stabilization of resin glue that will use and charge generation material.As organic solvent, for example, can mention alcohols solvent, sulfoxide kind solvent, ketones solvent, ether solvent, esters solvent or aromatic hydrocarbon solvent.

It is following with more preferably 0.1 μ m is above to 2 μ m that the film thickness of charge generation layer is preferably 5 μ m.

In addition, various types of emulsion, antioxidant, ultraviolet light absorber and plastifier randomly can be added in this charge generation layer.In addition, for held stationary ground electric charge (charge carrier) flows, charge generation layer can contain electron transport material (electronics is accepted material such as acceptor).

On charge generation layer, charge transport layer is set.

As the charge transport material that in electrophotographic photosensitive element of the present invention, uses, for example, can mention aforesaid triarylamine compounds, hydrazone compound, compound of styryl, stilbene compounds, pyrazoline compounds, oxazole compound, thiazolium compounds and triaryl methane compounds.In these, the compound of being represented by above-mentioned formula (4) is preferred.In addition, the content of the compound of being represented by above-mentioned formula (4) in charge transport layer preferably is not less than 10 quality %, with respect to the gross mass of whole charge transport materials in charge transport layer.

As the charge transport layer of electrophotographic photosensitive element superficial layer of the present invention comprise have by the constitutional repeating unit of above-mentioned formula (1) expression and by the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression as resin glue.As mentioned above, can other resin of blend.Resin glue that can blend is same as described above.

Charge transport layer can be by applying the charge transport layer coating fluid that obtains by dissolved charge transportation of substances and resin glue in solvent and being dried formation.

The ratio of charge transport material and resin glue preferably falls in the scope of 4: 10 to 20: 10 (mass ratio) and more preferably falls in the scope of 5: 10 to 12: 10 (mass ratio).

As the solvent that in the charge transport layer coating fluid, uses, for example, can mention ketones solvent such as acetone and MEK; Esters solvent such as methyl acetate and ethyl acetate; Ether solvent such as tetrahydrofuran, diox, dimethoxymethane and dimethoxy-ethane; With aromatic hydrocarbon solvent such as toluene, dimethylbenzene and chlorobenzene.Can be separately or use these solvents as two or more potpourri.In these solvents,, preferably use ether solvent and aromatic hydrocarbon solvent from the angle of resin dissolves.

The film thickness of charge transport layer be preferably 5 μ m above to 50 μ m and more preferably more than the 10 μ m to 35 μ m.

In addition, can in this charge transport layer, randomly add antioxidant, ultraviolet light absorber and plastifier etc.

Can in each layer of electrophotographic photosensitive element of the present invention, add various adjuvants.As adjuvant, for example, can mention deterioration preventing agent such as antioxidant, ultraviolet light absorber and light stabilizer, particulate is organic fine particles and inorganic particles for example.As deterioration preventing agent, for example, can mention that hindered phenol is that antioxidant, hindered amine are the antioxidant of light stabilizer, sulfur atom-containing and the antioxidant that contains phosphorus atoms.As organic fine particles, for example, can mention resin particle, ps particle and polymeric resin particles such as the polyvinyl resin particle of contain fluorine atoms.As inorganic particles, for example, can mention metal oxide such as silicon dioxide and aluminium oxide.

When applying coating fluid when forming each layer,, can use dip coating, spraying process, spin-coating method, rolling method, Meyer rod (Mayer-bar) to be coated with method and knife coating as coating process.

Fig. 3 illustrates the figure that schematically illustrates the electronic photographing device structure that is provided with the handle box with electrophotographic photosensitive element of the present invention.

In Fig. 3, cylindric electrophotographic photosensitive element 1 is driven with predetermined peripheral speed around axle 2 along the direction of arrow and rotates.

(charging device: charging roller etc.) 3 are just charging or the negative predetermined potential that charges to by charging device equably with the surface of the electrophotographic photosensitive element 1 that is driven and rotates.Next, be exposed to light (image exposure light) 4 by the emission of light exposure device (not shown in FIG.), for example, slit exposure light and laser beam flying exposure light.In this way, the continuous electrostatic latent image that forms corresponding to the expection image on the surface of electrophotographic photosensitive element 1.

The toner development that comprises in the developer of electrostatic latent image by developing apparatus 5 that will form on electrophotographic photosensitive element 1 surface becomes toner image.Next, will form and be carried on toner image on the electrophotographic photosensitive element 1 by come continuously transfer printing to transfer materials (paper etc.) P from the transfer bias of transfer device (transfer roll) 6.Note, this transfer materials P with the synchronous mode of electrophotographic photosensitive element 1 rotation, take out and be fed to contact site between electrophotographic photosensitive element 1 and the transfer device 6 from transfer materials feedway (not shown).

The transfer materials P of toner image that has transfer printing on it from electrophotographic photosensitive element 1 surface isolation, and is imported in the fixing device 8 of photographic fixing image wherein.In this way, the material (printout, copy) that will have image formed thereon is discharged described equipment as printed matter.

After the transfer printing toner image, the surface of electrophotographic photosensitive element 1 is cleaned by means of removing residual developer (toner) by cleaning device (cleaning balde) 7.Next, make the surface be exposed to pre-exposure light (not shown) by pre-exposure equipment (not shown) emission, thereafter, be recycled and reused for image and form to remove electric charge.Note, as shown in Figure 3, when charging device 3 when adopting the contact charging device of charging roller etc., always essentially want above-mentioned pre-exposure light.

The for example above-mentioned electrophotographic photosensitive element 1 of a plurality of structural details, charging device 3, developing apparatus 5, transfer device 6 and cleaning device 7 are installed in the container, and are combined into one as handle box.This handle box is removable installed in electronic photographing device main body such as duplicating machine and laser beam printer.In Fig. 3, electrophotographic photosensitive element 1, charging device 3, developing apparatus 5 and cleaning device 7 are remained in the box integratedly and as handle box 9, described handle box 9 is removable installed in the electronic photographing device main body by use guide piece (guide) 10 tracks as the electronic photographing device main body.

Fig. 4 illustrates the figure of the structure that schematically illustrates color electronography equipment (tandem moor), and this color electronography equipment is equipped with the handle box with electrophotographic photosensitive element of the present invention.

In Fig. 4,

Reference numeral

1Y, 1M, 1C and 1K represent cylindric electrophotographic photosensitive element (first to fourth look electrophotographic photosensitive element), and its direction of following the arrow around axle 2Y, 2M, 2C and 2K respectively is driven with predetermined circle speed and rotates.

By the first look charging device (charging device: charging roller) 3Y first look that will be driven and rotate with the surface of electrophotographic photosensitive element 1Y equably plus or minus charge to predetermined potential.Next, the surface is exposed to from exposure device (not shown) exposure light (image exposure light) 4Y of slit exposure and laser beam flying exposure emission for example.Exposure light 4Y is corresponding to the first colour content image (for example, yellow component-part diagram picture) of the coloured image of expectation.By this way, on the surface of the first color electronic photographing Electrifier frame, photoreceptor 1Y, form in turn corresponding to first colour cell of the first colour content image of expecting color image and divide electrostatic latent image (yellow color component electrostatic latent image).

Transfer materials transfer member (transfer materials conveying belt) 14 directions of following the arrow by idler roller (stretching/extending rollers) 12 tensionings are driven with the peripheral speed peripheral speed (for example, the 97-103% of the peripheral speed of first to fourth color electronic photographing Electrifier frame,

photoreceptor

1Y, 1M, 1C and 1K) much at one with first to fourth color electronic photographing Electrifier frame,

photoreceptor

1Y, 1M, 1C and 1K and rotate.In addition, carried (absorption) by transfer materials transfer member 14 by static from transfer materials (paper etc.) P of transfer materials feedway 17 feedings, and be sent to the contact site between first to fourth color electronic photographing Electrifier frame,

photoreceptor

1Y, 1M, 1C and 1K and the transfer materials transfer member in turn.

The toner development that first colour cell that forms on the first color electronic photographing Electrifier frame, photoreceptor 1Y surface divides electrostatic latent image to pass through the first look developing apparatus 5Y is to form the first colour toners image (yellow toner image).Subsequently, will be carried on the lip-deep first colour toners image of the first color electronic photographing Electrifier frame, photoreceptor 1Y is transferred in turn by the transfer bias from first look transfer device (transfer roll etc.) 6Y and is carried on the transfer materials transfer member 14 and through the transfer materials P in the space between the first color electronic photographing Electrifier frame, photoreceptor 1Y and the first look transfer device 6Y.

After with the first colour toners image transfer printing, remove the surface that residual toner cleans the first color electronic photographing Electrifier frame, photoreceptor 1Y by first look cleaning device (cleaning balde) 7Y, and it is recycled and reused for the formation first colour toners image.

With the first color electronic photographing Electrifier frame, photoreceptor 1Y, the first look charging device 3Y, the first look exposure device, the first look developing apparatus 5Y and the first look transfer device 6Y that are used to launch corresponding to the exposure light 4Y of the first colour content image be generically and collectively referred to as the first color image formation portion (section).

With the second color image formation portion, image three-colo(u)r formation portion, four-color image formation portion with the first color image imaging device in identical mode operate, this second color image formation portion has the second color electronic photographing Electrifier frame, photoreceptor 1M, the second look charging device 3M, is used to launch the second look exposure device, the second look developing apparatus 5M and the second look transfer device 6M corresponding to the exposure light 4M of the second colour content image; This image three-colo(u)r formation portion has the 3rd color electronic photographing Electrifier frame, photoreceptor 1C, the 3rd look charging device 3C, is used to launch tricolor exposing device, the 3rd look developing apparatus 5C and the 3rd look transfer device 6C corresponding to the exposure light 4C of the 3rd colour content image; This four-color image formation portion has the 4th color electronic photographing Electrifier frame, photoreceptor 1K, the 4th look charging device 3K, is used to launch the 4th look exposure device, the 4th look developing apparatus 5K and the 4th look transfer device 6K corresponding to the exposure light 4K of the 4th colour content image.More specifically, the second colour toners image (magenta toner image), three color scheme toner image (cyan toner image) and the 4th colour toners image (black toner image) are transferred in turn the transfer materials P that carries and have the transfer printing first colour toners image thereon by transfer materials transfer member 14.By this way, on the transfer materials P of carrying, form synthetic toner image on by transfer materials transfer member 14 corresponding to the color image of expectation.

The transfer materials P that will have a synthetic toner image formed thereon is from the surface isolation of transfer materials transfer member 14 and introduce the fixing device 8 of photographic fixing image wherein.By this way, the material (printout, copy) that will have color image formed thereon is exported as printed matter (printed matter) slave unit.

In addition, after removing residual toner by first look to the, four

look charging device

7Y, 7M, 7C and 7K, the electric charge on the surface of first look to the, four color electronic photographing Electrifier frame,

photoreceptor

1Y, 1M, 1C and 1K can be eliminated by the pre-exposure from pre-exposure equipment.Yet when first look to the, four

look charging device

3Y, 3M, 3C and 3K were to use the contact charging device of charging roller as shown in Figure 4, pre-exposure was always unessential.

At structural detail for example in electrophotographic photosensitive element, charging device, developing apparatus, transfer device and the cleaning device, be installed in a plurality of structural units in the container and be assembled into handle box.This handle box is removable installed in electronic photographing device main body for example duplicating machine and laser beam printer.In Fig. 4, in the box of each image forming part, the integrated one that is assembled into of electrophotographic photosensitive element, charging device, developing apparatus and charging device also is used as handle box.By using for example track of electronic photographing device main body of guide piece (not shown),

handle box

9Y, 9M, 9C and 9K are removable installed in the electronic photographing device main body.

(embodiment)

To the present invention more specifically be described by the mode of specific embodiment.Yet, the invention is not restricted to these embodiment.Note " part " is meant " mass parts " among the embodiment.

(embodiment 1)

The aluminium cylinder that will have diameter 30mm and length 260.5mm is as supporting mass.

Then, with 10 parts of SnO ₂The solvent mixture of barium sulphate (conductive particle), 2 parts of titanium dioxide (controlling resistance pigment), 6 parts of phenolics (resin glue), 0.001 part of silicone oil (levelling agent) and methyl alcohol (4 parts)/methoxypropanol (16 parts) of-coating is used to prepare the conductive layer coating fluid.

The conductive layer coating fluid is applied on the supporting mass by dip-coating, and by hardening in 30 minutes in 140 ℃ of following heat curings (thermal setting), thereby conductive layer formed with 15 μ m film thicknesses.

Then, N-methoxy nylon (3 parts) and nylon copolymer (3 parts) are dissolved in the solvent mixture of methyl alcohol (65 parts)/normal butyl alcohol (30 parts), with preparation middle layer coating fluid.

The middle layer coating fluid is applied on the conductive layer by dip-coating, and descended dry 10 minutes, thereby acquisition has the middle layer of 0.7 μ m film thickness at 100 ℃.

Then, (it ° is 7.5 °, 9.9 °, 16.3 °, 18.6 ° in Bragg angle (in CuK α characteristic X-ray diffraction) 2 θ ± 0.2 with 10 parts of crystallization shape hydroxy gallium phthalocyanines (charge generation material), 25.1 ° and 28.3 ° locate to have strong peak) be added into by with 5 parts of polyvinyl butyral resins (trade name: SLEC BX-1, resin glue, by Sekisui ChemicaiCo., Ltd. makes) be dissolved in the solution that obtains in the cyclohexanone (250 parts).Under 23 ± 3 ℃ atmosphere, the sand mill equipment that has the beaded glass of diameter 1mm by use disperseed 1 hour with this potpourri.After the dispersion, add ethyl acetate (250 parts) with preparation charge generation layer coating fluid.

The charge generation layer coating fluid is applied on the middle layer by dip-coating, and descended dry 10 minutes, thereby form charge generation layer with 0.26 μ m film thickness at 100 ℃.

Then, 1 part of compound (charge transport material) by above-mentioned formula (4-1) expression, 9 parts are dissolved in the solvent mixture of dimethoxymethane (20 parts) and monochloro-benzene (60 parts) by synthetic vibrin A1 (resin glue) in the compound (charge transport material) of following formula (CTM-1) expression and the 10 parts of synthesis examples 1, to prepare the charge transport layer coating fluid.

The charge transport layer coating fluid is applied on the charge generation layer by dip-coating, and descended dry 1 hour, thereby acquisition has the charge transport layer of 19 μ m film thicknesses at 120 ℃.

By this way, manufacturing has the electrophotographic photosensitive element of charge transport layer as superficial layer.

Then, evaluation will be described.

Carry out about 2, under the repeated use situation of 000 paper the relative value of the variation (potential change) of clear zone current potential, initial moment and the relative value of torque under the repeated use situation of 2,000 paper and when measuring torque in the evaluation of the lip-deep observation of electrophotographic photosensitive element.

As valuator device, the laser beam printer LBP-2510 that transformation is made by Canon Inc. (charging (once charging): the contact charging system, processing speed: thus 94.2mm/s) can regulate the charge potential (dark space current potential) of electrophotographic photosensitive element and come into operation.In addition, will be set at 25 ° with respect to the contact angle on electrophotographic photosensitive element surface by the cleaning balde of urethane rubber manufacturing, and its contact pressure will be set at 35g/cm.

Evaluation is that 23 ℃ and relative humidity are to carry out under 50% the environment in temperature.

The evaluation of＜potential change 〉

The exposure (exposure of image) of the lasing light emitter (780nm) of setting valuator device is so that electrophotographic photosensitive element surface light quantity is 0.3 μ J/cm ²

The surface potential of electrophotographic photosensitive element (dark space current potential and clear zone current potential) is positioned at the fixing consequently potential measurement probe of described anchor clamps apart from the distance of electrophotographic photosensitive element edge 130mm by being measured in the position of developing apparatus by anchor clamps exchange developing apparatus.

The potential setting that with the dark space of electrophotographic photosensitive element is unexposed portion is-450V, applies laser then.Measurement is from the clear zone current potential of dark space current potential optical attenuation.

In addition, use A4 size plain paper, output image in turn on 2,000.Before and after the operation, estimate the variation of clear zone current potential.The results are shown in the row of potential change in the table 4.Notice that the test pattern of Shi Yonging has 5% printing rate herein.

＜the evaluation of torque value relatively 〉

Under the condition identical, measure the driving current value (current value A) of the turning motor that is used for electrophotographic photosensitive element with above potential change appreciation condition.During this is estimated, estimate the amount of the contact stress between electrophotographic photosensitive element and the cleaning balde.The size of the current value that obtains is represented the amount of the contact stress between electrophotographic photosensitive element and the cleaning balde.

In addition, be with comparing with the electrophotographic photosensitive element that obtains relative torque value according to following method manufacturing.

Have at 5: 5 by the constitutional repeating unit of above-mentioned formula (2-12) expression with by the vibrin (weight-average molecular weight 120 of the constitutional repeating unit of above-mentioned formula (2-24) expression except changing into as the vibrin A1 of the resin glue of the charge transport layer of the electrophotographic photosensitive element of embodiment 1 with mol ratio, 000) in addition, makes electrophotographic photosensitive element in the mode identical with embodiment 1.With this with comparing electrophotographic photosensitive element.

Use the contrast electrophotographic photosensitive element of making thus, measure the driving current value (current value B) of the turning motor of electrophotographic photosensitive element in the mode identical with embodiment 1.

Calculate thus obtained use according to the driving current value (current value A) of the electrophotographic photosensitive element of vibrin of the present invention with do not use according to the ratio between the driving current value (current value B) of the turning motor of the electrophotographic photosensitive element of vibrin A of the present invention.Institute's value of (current value A)/(current value B) is used relative torque value as a comparison.Increase/the minimizing of contact stress amount between the numeric representation electrophotographic photosensitive element of torque value and the cleaning balde relatively.The numerical value of torque value is more little relatively, and the contact stress amount between electrophotographic photosensitive element and the cleaning balde is low more.The results are shown in the row of the relative value of initial moment in the table 4.

Next, use A4 size plain paper, output image in turn on 2,000.Notice that the test pattern of Shi Yonging has 5% printing rate herein.

Be determined at repeated use (2,000) afterwards relative torque value thereafter.Estimate at repeated use (2,000) relative torque value afterwards in the mode identical with the relative value of initial moment.In the case, will contrast electrophotographic photosensitive element and be recycled and reused for 2,000.Use the driving current value of this moment, calculate the relative value of torque after reusing 2,000.The results are shown in the table 4 in the row of the relative torque values after 2,000.

(embodiment 2 to 8)

Except the resin glue of the charge transport layer among the embodiment 1 being changed into shown in the table 2 those, with embodiment 1 in identical mode make and estimate electrophotographic photosensitive element.The results are shown in the table 4.

(embodiment 9)

Carry out with embodiment 1 in identical step until forming charge generation layer.

Then, 5: 5 have by the constitutional repeating unit of above-mentioned formula (2-12) expression with mol ratio 1 part of compound (charge transport material), 9 parts of compounds (charge transport material), 8 parts of vibrin A 1 synthetic in synthesis example 1 and 2 parts and be dissolved in by the vibrin (weight-average molecular weight 120,000) of the constitutional repeating unit of above-mentioned formula (2-24) expression in the solvent mixture of dimethoxymethane (20 parts) and monochloro-benzene (60 parts) to prepare the charge transport layer coating fluid by above-mentioned formula (CTM-1) expression by above-mentioned formula (4-1) expression.

The charge transport layer coating fluid is applied on the charge generation layer by dip-coating, and at 120 ℃ of dry down charge transport layers that had 19 μ m film thicknesses in 1 hour with formation.For the charge transport layer that forms, do not observe have the siloxane position according to vibrin of the present invention (vibrin A1) in the gathering of charge transport material.

Estimate in the mode identical with embodiment 1.The results are shown in the table 4.

(embodiment 10)

Except will be in embodiment 9 vibrin A1 with respect to having at 5: 5 with mol ratio by the constitutional repeating unit of above-mentioned formula (2-12) expression with by the vibrin (weight-average molecular weight 120 of the constitutional repeating unit of above-mentioned formula (2-24) expression, 000) mixing ratio is changed into outside the mixing ratio shown in the table 2, makes and estimate electrophotographic photosensitive element in the mode identical with embodiment 9.The results are shown in the table 4.In embodiment 10, for the charge transport layer that forms, do not observe have the siloxane position according to vibrin of the present invention (vibrin A1) in the gathering of charge transport material.

(embodiment 11)

Carry out with embodiment 1 in identical step until obtaining charge generation layer.

Then, with 1 part of compound (charge transport material), 9 parts of compounds (charge transport material), 8 parts of vibrin A1 synthetic in synthesis example 1 and 2 parts of polycarbonate resin (weight-average molecular weight 120 that have by the constitutional repeating unit of above-mentioned formula (9-4) expression by above-mentioned formula (CTM-1) expression by above-mentioned formula (4-1) expression, 000) is dissolved in the solvent mixture of dimethoxymethane (20 parts) and monochloro-benzene (60 parts), with preparation charge transport layer coating fluid.

(embodiment 12 to 17)

Except the resin glue of the charge transport layer among the embodiment 1 is changed into shown in the table 2 those and use with the mixing ratio shown in the table 2, with embodiment 1 in identical mode make and estimate electrophotographic photosensitive element.The results are shown in the table 4.For the charge transport layer that in embodiment 16 and 17, forms, do not observe have the siloxane position according to vibrin of the present invention (vibrin B1) in the gathering of charge transport material.

(embodiment 18 to 22)

Except the resin glue of the charge transport layer among the embodiment 1 is changed into shown in the table 2 those and use with the mixing ratio shown in the table 2, with embodiment 1 in identical mode make and estimate electrophotographic photosensitive element.Yet, the electrophotographic photosensitive element that uses in the torque evaluation is by to make and to measure down: the resin glue of the charge transport layer of the contrast electrophotographic photosensitive element that will use in embodiment 1 is changed into the vibrin (weight-average molecular weight 130,000) that has by the constitutional repeating unit of above-mentioned formula (2-33) expression.The results are shown in the table 4.

(embodiment 23 to 29)

Except the resin glue of the charge transport layer among the embodiment 1 is changed into shown in the table 2 those and use with the mixing ratio shown in the table 2, and be outside the compound by above-mentioned formula (4-7) expression in addition with the charge transport substance change, with embodiment 1 in identical mode make and estimate electrophotographic photosensitive element.Yet, the electrophotographic photosensitive element that uses in the torque evaluation is by following manufacturing and measure: the resin glue of the charge transport layer of the contrast electrophotographic photosensitive element that will use in embodiment 1 is changed into the vibrin (weight-average molecular weight 130 that has by the constitutional repeating unit of above-mentioned formula (2-33) expression, 000), and in addition be compound by above-mentioned formula (4-7) expression with the charge transport substance change.The results are shown in the table 4.For the charge transport layer that in embodiment 27 to 29, forms, do not observe have the siloxane position according to vibrin of the present invention (vibrin H) in the gathering of charge transport material.

(embodiment 30 to 33)

Except the resin glue of the charge transport layer among the embodiment 1 is changed into shown in the table 2 those and use with the mixing ratio shown in the table 2, with embodiment 1 in identical mode make and estimate electrophotographic photosensitive element.Yet, the electrophotographic photosensitive element that uses in the torque evaluation is by following manufacturing and measure: the resin glue of the charge transport layer of the contrast electrophotographic photosensitive element that will use in embodiment 1 is changed into mol ratio to have by the constitutional repeating unit of above-mentioned formula (2-34) expression with by the vibrin (weight-average molecular weight 110,000) of the constitutional repeating unit of above-mentioned formula (2-24) expression at 7: 3.The results are shown in the table 4.

(embodiment 34)

Except the resin glue of the charge transport layer among the embodiment 1 is changed into shown in the table 2 those and use with the mixing ratio shown in the table 2, with embodiment 1 in identical mode make and estimate electrophotographic photosensitive element.Yet, the electrophotographic photosensitive element that uses in the torque evaluation is by following manufacturing and measure: the resin glue of the charge transport layer of the contrast electrophotographic photosensitive element that will use in embodiment 1 is changed into the vibrin (weight-average molecular weight 120,000) that has by the constitutional repeating unit of above-mentioned formula (2-1) expression.The results are shown in the table 4.

(embodiment 35)

Except the resin glue of the charge transport layer among the embodiment 1 is changed into shown in the table 2 those and use with the mixing ratio shown in the table 2, with embodiment 1 in identical mode make and estimate electrophotographic photosensitive element.Yet, the electrophotographic photosensitive element that uses in the torque evaluation is by following manufacturing and measure: the resin glue of the charge transport layer of the contrast electrophotographic photosensitive element that will use in embodiment 1 is changed into the vibrin (weight-average molecular weight 120,000) that has by the constitutional repeating unit of above-mentioned formula (2-2) expression.The results are shown in the table 4.

(embodiment 36)

Except the resin glue of the charge transport layer among the embodiment 1 is changed into shown in the table 2 those and use with the mixing ratio shown in the table 2, with embodiment 1 in identical mode make and estimate electrophotographic photosensitive element.Yet, the electrophotographic photosensitive element that uses in the torque evaluation is by following manufacturing and measure: the resin glue of the charge transport layer of the contrast electrophotographic photosensitive element that will use in embodiment 1 is changed into mol ratio to have by the constitutional repeating unit of above-mentioned formula (2-1) expression with by the vibrin (weight-average molecular weight 110,000) of the constitutional repeating unit of above-mentioned formula (2-24) expression at 3: 7.The results are shown in the table 4.

(embodiment 37)

Except the resin glue of the charge transport layer among the embodiment 1 is changed into shown in the table 2 those and use with the mixing ratio shown in the table 2, with embodiment 1 in identical mode make and estimate electrophotographic photosensitive element.Yet, the electrophotographic photosensitive element that uses in the torque evaluation is by following manufacturing and measure: the resin glue of the charge transport layer of the contrast electrophotographic photosensitive element that will use in embodiment 1 is changed into mol ratio to have by the constitutional repeating unit of above-mentioned formula (2-2) expression with by the vibrin (weight-average molecular weight 110,000) of the constitutional repeating unit of above-mentioned formula (2-24) expression at 3: 7.The results are shown in the table 4.

(comparative example 1)

Siloxane position content (in the gross mass of vibrin) be the vibrin A9 (weight-average molecular weight 120,000) of 1 quality % use in synthesis example 1, use by the diacyl halogen of above-mentioned formula (6-1) expression and by the diacyl halogen of above-mentioned formula (6-2) expression as diacyl halogen and use in synthesis example 1, use by the diol compound of above-mentioned formula (7-1) expression and control their consumptions when synthetic by the diol compound of above-mentioned formula (8-1) expression simultaneously as glycol and prepare.This is shown in Table 3.

Except the resin glue of the charge transport layer among the embodiment 1 is changed into the vibrin A9, with embodiment 1 in identical mode make and estimate electrophotographic photosensitive element.The results are shown in the table 4.

(comparative example 2)

Siloxane position content (in the gross mass of vibrin) be the vibrin A10 (weight-average molecular weight 160,000) of 40 quality % use in synthesis example 1, use by the diacyl halogen of above-mentioned formula (6-1) expression and by the diacyl halogen of above-mentioned formula (6-2) expression as diacyl halogen and use in synthesis example 1, use by the diol compound of above-mentioned formula (7-1) expression and control their consumptions when synthetic by the diol compound of above-mentioned formula (8-1) expression simultaneously as glycol and prepare.This is shown in Table 3.

Except the resin glue of the charge transport layer among the embodiment 1 is changed into the vibrin A10, with embodiment 1 in identical mode make and estimate electrophotographic photosensitive element.The results are shown in the table 4.For the charge transport layer that forms, observe the gathering of charge transport material in the resin with siloxane position (vibrin A10).

(comparative example 3)

Siloxane position content (in the gross mass of vibrin) be the vibrin T1 (weight-average molecular weight 120,000) of 20 quality % use in synthesis example 1, use by the diacyl halogen of above-mentioned formula (6-1) expression and by the diacyl halogen of above-mentioned formula (6-2) expression as diacyl halogen and use by the diol compound of following formula (7-8) expression and control their consumptions when synthetic simultaneously as glycol and prepare by the diol compound of above-mentioned formula (8-1) expression.Vibrin T1 for containing with mol ratio by the constitutional repeating unit of following formula (P-1) expression and the constitutional repeating unit of being represented by following formula (P-2) at 5: 5; And contain at 5: 5 by the constitutional repeating unit of above-mentioned formula (2-12) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2-24) expression with mol ratio.

Except the resin glue of the charge transport layer among the embodiment 1 is changed into the vibrin T1, with embodiment 1 in identical mode make electrophotographic photosensitive element.This is shown in Table 3.Estimate in the mode identical with embodiment 1.The results are shown in the table 4.

(comparative example 4)

Siloxane position content (in the gross mass of vibrin) be the vibrin T2 (weight-average molecular weight 120,000) of 20 quality % use in synthesis example 1, use by the diacyl halogen of above-mentioned formula (6-1) expression and by the diacyl halogen of above-mentioned formula (6-2) expression as diacyl halogen and use by the diol compound of following formula (7-9) expression and control their consumptions when synthetic by the diol compound of above-mentioned formula (8-1) expression simultaneously as glycol and synthesize.Vibrin T2 for containing with mol ratio by the constitutional repeating unit of following formula (P-3) expression and the constitutional repeating unit of being represented by following formula (P-4) at 5: 5; And contain at 5: 5 by the constitutional repeating unit of above-mentioned formula (2-12) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2-24) expression with mol ratio.

Except the resin glue of the charge transport layer among the embodiment 1 is changed into the vibrin T2, with embodiment 1 in identical mode make electrophotographic photosensitive element.This is shown in Table 3.Estimate in the mode identical with embodiment 1.The results are shown in the table 4.

For the charge transport layer that forms, observe the gathering of charge transport material in the resin with siloxane position (vibrin T2).

(comparative example 5)

Siloxane position content (in the gross mass of vibrin) be the vibrin U (weight-average molecular weight 120,000) of 20 quality % use in synthesis example 1, use by the diacyl halogen of above-mentioned formula (6-1) expression and by the diacyl halogen of above-mentioned formula (6-2) expression as diacyl halogen and use by the diol compound of following formula (7-10) expression and control their consumptions when synthetic simultaneously as glycol and prepare by the diol compound of above-mentioned formula (8-1) expression.Vibrin U for containing with mol ratio by the constitutional repeating unit of following formula (P-5) expression and the constitutional repeating unit of being represented by following formula (P-6) at 5: 5; And contain at 5: 5 by the constitutional repeating unit of above-mentioned formula (2-12) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2-24) expression with mol ratio.

Except the resin glue of the charge transport layer among the embodiment 1 is changed into the vibrin U, with embodiment 1 in identical mode make electrophotographic photosensitive element.This is shown in Table 3.Estimate in the mode identical with embodiment 1.The results are shown in the table 4.

(comparative example 6)

Siloxane position content (in the gross mass of vibrin) be the vibrin V (weight-average molecular weight 120,000) of 20 quality % use in synthesis example 1, use by the diacyl halogen of above-mentioned formula (6-1) expression and by the diacyl halogen of above-mentioned formula (6-2) expression as diacyl halogen and use by the diol compound of following formula (7-11) expression and control their consumptions when synthetic simultaneously as glycol and prepare by the diol compound of above-mentioned formula (8-1) expression.Vibrin V for containing with mol ratio by the constitutional repeating unit of following formula (P-7) expression and the constitutional repeating unit of being represented by following formula (P-8) at 5: 5; And contain at 5: 5 by the constitutional repeating unit of above-mentioned formula (2-12) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2-24) expression with mol ratio.

Except the resin glue of the charge transport layer among the embodiment 1 is changed into the vibrin V, with embodiment 1 in identical mode make electrophotographic photosensitive element.This is shown in Table 3.Estimate in the mode identical with embodiment 1.The results are shown in the table 4.

For the charge transport layer that forms, observe the gathering of charge transport material in the resin with siloxane position (vibrin V).

(comparative example 7)

Siloxane position content (in the gross mass of vibrin) be the vibrin W1 (weight-average molecular weight 100,000) of 20 quality % use in synthesis example 1, use by the diacyl halogen of above-mentioned formula (6-1) expression and by the diacyl halogen of above-mentioned formula (6-2) expression as diacyl halogen and use by the diol compound of following formula (7-10) expression with by the diol compound of above-mentioned formula (8-1) expression and control their consumption preparations when synthetic simultaneously as glycol.Vibrin W 1 for containing with mol ratio by the constitutional repeating unit of following formula (P-9) expression and the constitutional repeating unit of being represented by following formula (P-10) at 5: 5; And contain at 5: 5 by the constitutional repeating unit of above-mentioned formula (2-12) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2-24) expression with mol ratio.

Except the resin glue of the charge transport layer among the embodiment 1 is changed into the vibrin W1, with embodiment 1 in identical mode make electrophotographic photosensitive element.This is shown in Table 3.Estimate in the mode identical with embodiment 1.The results are shown in the table 4.

(comparative example 8)

Siloxane position content (in the gross mass of vibrin) be the vibrin W2 (weight-average molecular weight 80,000) of 20 quality % use in synthesis example 1, use by the diacyl halogen of above-mentioned formula (6-1) expression and by the diacyl halogen of above-mentioned formula (6-2) expression as diacyl halogen and use by the diol compound of following formula (7-13) expression with by the diol compound of above-mentioned formula (8-1) expression and control their consumption preparations when synthetic simultaneously as glycol.Vibrin W2 for containing with mol ratio by the constitutional repeating unit of following formula (P-11) expression and the constitutional repeating unit of being represented by following formula (P-12) at 5: 5; And contain at 5: 5 by the constitutional repeating unit of above-mentioned formula (2-12) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2-24) expression with mol ratio

Except the resin glue of the charge transport layer among the embodiment 1 is changed into the vibrin W2, with embodiment 1 in identical mode make electrophotographic photosensitive element.This is shown in Table 3.Estimate in the mode identical with embodiment 1.The results are shown in the table 4.

(comparative example 9)

Except the resin glue of the charge transport layer among the embodiment 1 being changed into the vibrin X that puts down in writing among the Japanese Patent Application Laid-Open 2003-302780 (it for having with mol ratio by the constitutional repeating unit of following formula (P-13) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2-15) expression at 15: 85), with embodiment 1 in identical mode make electrophotographic photosensitive element.This is shown in Table 3.Estimate in the mode identical with embodiment 1.The results are shown in the table 4.

(comparative example 10)

As the resin glue of charge transport layer among the embodiment 1, synthesizing polyester resin Y, described vibrin Y has by the constitutional repeating unit of following formula (P-14) expression and the constitutional repeating unit of being represented by following formula (P-15) with mol ratio at 5: 5; And have at 5: 5 by the constitutional repeating unit of above-mentioned formula (2-12) expression with by the constitutional repeating unit of above-mentioned formula (2-23) expression with mol ratio.The content at siloxane position is 30 quality % in the synthetic resin.

Except the resin glue of the charge transport layer among the embodiment 1 is changed into the vibrin Y, with embodiment 1 in identical mode make electrophotographic photosensitive element.This is shown in Table 3.Estimate in the mode identical with embodiment 1.The results are shown in the table 4.For the charge transport layer that forms, observe the gathering of charge transport material in the resin with siloxane position (vibrin Y).

(comparative example 11)

Synthesizing polyester resin Z, described vibrin Z have by the constitutional repeating unit of above-mentioned formula (2-12) expression with by the constitutional repeating unit of above-mentioned formula (2-24) expression and the structure by following formula (7-14) expression with introducing end.The content at siloxane position is 1.2 quality % in synthetic resin.

Except the resin glue of the charge transport layer among the embodiment 1 is changed into the vibrin Z, with embodiment 1 in identical mode make electrophotographic photosensitive element.This is shown in Table 3.Estimate in the mode identical with embodiment 1.The results are shown in the table 4.

(comparative example 12)

Have at 5: 5 by the constitutional repeating unit of above-mentioned formula (9-4) expression with by the polycarbonate resin A of the constitutional repeating unit of following formula (P-16) expression and it is as shown in table 3 with the vibrin that has the constitutional repeating unit of representing by the constitutional repeating unit of above-mentioned formula (2-12) expression with by above-mentioned formula (2-24) with mol ratio at 5: 5 mixes with mol ratio except synthetic, with embodiment 1 in identical mode make electrophotographic photosensitive element.This is shown in Table 3.Estimate in the mode identical with embodiment 1.The results are shown in the table 4.

Table 2

In table 2, " Resin A (vibrin) " is meant to have by the constitutional repeating unit of above-mentioned formula (1) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression.

In table 2, " the mass ratio A (quality %) of siloxane " is meant the content (quality %) at siloxane position in " Resin A (vibrin) ".

In table 2, " resin B (resin with different structure) " is meant the resin that does not contain the siloxane position.

In table 2, " the mass ratio B (quality %) of siloxane " is meant the gross mass with respect to the whole resin glues that comprise in charge transport layer, the content (quality %) at siloxane position in " Resin A (vibrin) ".

Table 3

In table 3, " Resin A (vibrin) " is meant the content of the resin with siloxane position.

In table 3, " the mass ratio A (quality %) of siloxane " is meant the content (quality %) at siloxane position in " Resin A ".

In table 3, " resin B (resin with different structure) " is meant the resin that does not contain the siloxane position.

In table 3, " the mass ratio B (quality %) of siloxane " is meant the gross mass with respect to the whole resin glues that comprise in charge transport layer, the content at siloxane position (quality %) in " Resin A ".

Table 4

Relatively proof between embodiment and the comparative example 1, when siloxane when all the mass ratio of resin glues is low in respect to charge transport layer with respect to the mass ratio of the vibrin in the charge transport layer and siloxane, can not obtain to relax the effect of sufficient of contact stress.

In addition, relatively proof between embodiment and the comparative example 2 when siloxane is high with respect to the mass ratio of the vibrin in the charge transport layer, becomes insufficient with the compatibility of charge transport material, and the charge transport material aggregation causes potential change in the resin with siloxane position.

In addition, the relatively proof between embodiment and the comparative example 3 when the vibrin that has the siloxane position in charge transport layer has the repetition average at little siloxane position, can not obtain to relax the effect of sufficient of contact stress.This means that the effect that relaxes contact stress depends on the length of siloxane chain and changes.

Yet, the relatively proof between embodiment and the comparative example 4, when the vibrin that has the siloxane position in charge transport layer had the repetition average at big siloxane position, it is big that potential change becomes, the characteristic degradation of electrophotographic photosensitive element.This is because when the siloxane chain length at siloxane position is grown, and assembles in the resin that contains the siloxane position with the compatibility reduction and the charge transport material of charge transport material.

Therefore, relax contact stress and compatibility gratifying and the charge transport material, importantly have the repetition average (siloxane chain length) at suitable siloxane position in order to keep evenly mutually.

In addition, the relatively proof between embodiment and the comparative example 5, the bonding position that depends on the phenylene position at bonding siloxane position and dicarboxylic acid position produces property difference.In the bonding mode (at para-linkage) at the phenylene position shown in the comparative example 5, the siloxane position relatively poor with the compatibility of charge transport material is arranged as polymer chain more linearly.For this reason, infer, in the resin that contains the siloxane position, assemble with the compatibility reduction and the charge transport material of charge transport material.In the bonding mode that illustrates in an embodiment (at the ortho position bonding), think because the siloxane position non-linearly is arranged as polymer chain, so compatibility is higher and stability of characteristicsization.

In addition, the relatively confirmation between embodiment and the comparative example 6, whether two ends that depend at the siloxane position exist alkylidene, occurrence features difference.This hint, as shown in comparative example 6, under the situation of siloxane position and phenylene position Direct Bonding, the compatibility of siloxane position and charge transport material significantly descends; Yet when having alkylidene, compatibility worsens generation hardly.Because the siloxane position has alkylidene at two ends, relatively freely modified structure improves compatibility.

In addition, the relatively confirmation between embodiment and the comparative example 7 when the siloxane position forms ring texture, almost the effect that does not obtain to relax contact stress.Usually known, the effect that relaxes contact stress is by existing the performance of siloxane position from the teeth outwards.Have at the siloxane position under the situation of linear chain structure, the glass transition temperature at siloxane position is low, thereby is easy to change the structure at siloxane position.Therefore, can be increased in the number at the siloxane position of surface existence.

Yet if the siloxane position has ring texture, this siloxane structure is compared with linear chain structure hardly and is changed.Thereby think that above-mentioned property difference takes place.

In addition, the relatively confirmation between embodiment and the comparative example 8 when the siloxane position has branched structure, can obtain the effect of gratifying mitigation contact stress; Yet become not enough with the compatibility of charge transport material, produce potential change.As mentioned above, this infers due to the fact that: although can not clearly observe the gathering of charge transport material, the charge transport material has the structure of aromatic rings, and is not high for the compatibility at siloxane position.

In addition, the relatively confirmation between embodiment and the comparative example 9, the effect of potential stability and mitigation contact stress is owing to the bonding mode of the phenylene that will be bonded to dicarboxylic acid is different and different.(embodiment) is different with alkylidene-oxygen atom structure in the alkylidene-methylene structure (comparative example 9) of phenylene ortho position bonding.Because it is sterically hindered, infer that this structure is relatively fixing in alkylidene-methylene.As a result, think different with the compatibility with the charge transport material of reflection potential stability, different with the effect of the mitigation contact stress that causes by moving freely of siloxane chain.In addition, in charge transport layer, have high siloxane and can imagine that with respect to the resin of the mass ratio of vibrin influencing characteristic worsens.

In addition, the relatively confirmation between embodiment and the comparative example 10, when carboxylic acid Direct Bonding during to the siloxane position, the compatibility of siloxane position and charge transport material significantly worsens.

In addition, relatively proof between embodiment and the comparative example 11, when only at one end having siloxane structure, structurally, siloxane is low with respect to the mass ratio of the whole resin glues in the charge transport layer with respect to the mass ratio and the siloxane of the vibrin in the charge transport layer, thereby can not obtain to relax the effect of contact stress.

In addition, the relatively proof between embodiment and the comparative example 12, when the polycarbonate resin with siloxane structure and vibrin were used in combination, the effect that relaxes contact stress was not lasting.Think that this is because the compatibility between the above-mentioned resin reduces and polycarbonate resin with siloxane structure may migrate to the surface.

(embodiment 38)

The electrophotographic photosensitive element that to make in the mode identical with embodiment 1 carries out surface working by the crimping shape transferred thereon/process equipment of use mould shown in Figure 2, and the shape transferred thereon mould shown in Fig. 5 wherein is set.During processing, the temperature of electrophotographic photosensitive element and mould is controlled under 110 ℃.Carry out shape transferred thereon with the exert pressure mould of 4MPa simultaneously by rotating electron photosensitive member along the circumferential direction.In Fig. 5, (1) illustrates mold shape and (2) observed from the top mold shape of observing from the side is shown.The mould that is shown among Fig. 5 has cylindrical shape.Major axis footpath D is 2.0 μ m, and height F is that the interval E between 6.0 μ m and mould and the mould is 1.0 μ m.

About the electrophotographic photosensitive element of making by said method, observe the surface by using super depth profile measuring microscope VK-9500 (making) by Keyence Corporation.The electrophotographic photosensitive element that will measure is placed on transforms it with on the platform of fixing its cylindric supporting mass.The 130mm distance is observed the surface in distance electrophotographic photosensitive element upper end.At this moment, be 50 times by the enlargement ratio of setting object lens and set square (10, the 000 μ m of 100 μ m on electrophotographic photosensitive element surface ²) the zone be that the visual field is measured.Measure observed depressed part in the visual field by the operational analysis process analysis.

About each depressed part in the visual field, the shape of meter face, major axis footpath (Rpc among Fig. 6) and the degree of depth (Rdv among Fig. 6).Confirm to have formed that to have major axis directly be that 2.0 μ m and mean depth are the depressed part (being shown among Figure 16) of 1.2 μ m.At Fig. 6 the arrangement of depressed part is shown, (1) is that figure and (2) of observing the electrophotographic photosensitive element surface from the top are the sectional view of depressed part.In addition, be that 1.0 μ m form depressed part with interval (I among Fig. 6).When calculate its area than the time, it is 46%.Resin composition in the charge transport layer that uses in embodiment 41 is shown in table 5.

Estimate the electrophotographic photosensitive element of acquisition in the mode identical with embodiment 1.The results are shown in the table 6.

(embodiment 39 to 41)

Except change is applied to the pressure of mould, will with embodiment 12,30 and 31 in the electrophotographic photosensitive element made of identical mode with embodiment 38 in identical mode carry out surface working.Observe the surface in the mode identical with embodiment 38.As a result, confirm, on the surface of electrophotographic photosensitive element, form following depressed part (as shown in Figure 6) respectively.

Embodiment 39: the average major axis footpath: 2.0 μ m, and mean depth: 1.4 μ m,

Embodiment 40: average major axis footpath: 2.0 μ m, mean depth: 0.8 μ m and

Embodiment 41: average major axis footpath: 2.0 μ m, mean depth: 0.9 μ m.

In addition, be that 1.0 μ m form depressed part with interval I.The resin composition that uses in the charge transport layer of embodiment 39-41 is shown in table 5.

With with embodiment 12,30 and 31 in identical mode estimate electrophotographic photosensitive element.The results are shown in the table 6.

(embodiment 42)

With with embodiment 1 in identical mode, on supporting mass, form conductive layer, middle layer and charge generation layer.

Then, by preparing the charge transport layer coating fluid in the solvent mixture that 1 part of compound (charge transport material) by above-mentioned formula (4-1) expression, 9 parts is dissolved in dipropylene glycol (2 parts), dimethoxymethane (18 parts) and monochloro-benzene (60 parts) by the compound (charge transport material) of above-mentioned formula (CTM-1) expression and 10 parts of vibrin A1 (resin glue) synthetic in synthesis example 1.

The charge transport layer coating fluid is applied on the charge generation layer and with the charge transport layer coating fluid by dip-coating is applied on the supporting mass.Apply the step of charge transport layer coating fluid under the following conditions: relative humidity be 50% and environment temperature be 25 ℃.After finishing application step 180 (180) seconds, the supporting mass that is coated with the charge transport layer coating fluid is placed in the blast drier that is preheated to 120 ℃.Carry out dehydration and had the charge transport layer of 19 μ m film thicknesses in 60 minutes with formation.

By this way, make and to have charge transport layer as the superficial layer and the electrophotographic photosensitive element of the depressed part of formation in its surface.The resin composition of the charge transport layer that uses in embodiment 42 is shown in Table 5.

With the mode surface measurements shape identical with embodiment 38.As a result, confirm with per 10,000 μ m ²The unit area of (100 μ m are square) is that 1,500 ratio forms that to have average major axis directly be that 2.5 μ m and mean depth are the depressed part of 1.2 μ m.

Estimate thus obtained electrophotographic photosensitive element in the mode identical with embodiment 1.The results are shown in the table 6.

(embodiment 43)

Except the vibrin A1 that will be among the embodiment 42 uses changes into the vibrin B1, with embodiment 42 in identical mode make electrophotographic photosensitive element.The resin composition of the charge transport layer that uses in embodiment 43 is shown in Table 5.

With the mode surface measurements shape identical with embodiment 38.As a result, confirm with per 10,000 μ m ²The unit area of (100 μ m are square) is that 1,200 ratio forms that to have average major axis directly be that 2.0 μ m and mean depth are the depressed part of 1.0 μ m.

(embodiment 44 to 45)

With with embodiment 1 in identical mode on supporting mass, form conductive layer, middle layer and charge generation layer.

Except be the compound of representing by above-mentioned formula (4-7) as the resin glue of charge transport layer with the charge transport substance change with the resin shown in the table 5, with embodiment 42 in identical mode make electrophotographic photosensitive element.The resin composition of the charge transport layer that uses in embodiment 44 and 45 is shown in Table 5.

With the mode surface measurements shape identical with embodiment 38.As a result, confirm respectively with per 10,000 μ m ²The unit area of (100 μ m are square) is that 1,200 and 1,400 ratio forms following depressed part on the electrophotographic photosensitive element surface.

Embodiment 44: average major axis footpath: 2.4 μ m, mean depth: 1.5 μ m and

Embodiment 45: average major axis footpath: 1.8 μ m, mean depth: 1.2 μ m.

With with embodiment 32 and 33 in identical mode estimate the electrophotographic photosensitive element of acquisition like this.The results are shown in the table 6.

(embodiment 46 to 49)

Except the vibrin A 1 that will be among the embodiment 42 uses changes into the resin that is shown in Table 5, with embodiment 42 in identical mode make electrophotographic photosensitive element.The resin composition of the charge transport layer that uses in embodiment 46-49 is shown in Table 5.

With the mode surface measurements shape identical with embodiment 38.As a result, confirm respectively with per 10,000 μ m ²The unit area of (100 μ m are square) is that 1,200,1,200,1,000 and 1,400 ratio forms following depressed part on the electrophotographic photosensitive element surface.

Embodiment 46: the average major axis footpath: 2.5 μ m, and mean depth: 1.2 μ m,

Embodiment 47: the average major axis footpath: 2.3 μ m, and mean depth: 1.4 μ m,

Embodiment 48: average major axis footpath: 2.8 μ m, mean depth: 1.5 μ m and

Embodiment 49: average major axis footpath: 1.8 μ m, mean depth: 1.2 μ m.

Estimate electrophotographic photosensitive element in the mode identical with embodiment 1.The results are shown in the table 6.

Table 5

In table 5, " Resin A (vibrin) " is meant to have by the constitutional repeating unit of above-mentioned formula (1) expression with by the vibrin of the constitutional repeating unit of above-mentioned formula (2) expression.

In table 5, " the mass ratio A (quality %) at siloxane position " is meant the content (quality %) at the siloxane position of " Resin A (vibrin) ".

In table 5, " resin B (resin with different structure) " is meant the resin that does not contain the siloxane position.

In table 5, " the mass ratio B (quality %) of siloxane " is meant the gross mass with respect to the whole resin glues that comprise, the content (quality %) at the siloxane position of " Resin A (vibrin) " in charge transport layer.

Table 6

(embodiment 50)

The aluminium cylinder that will have diameter and be 24mm and length and be 246mm is as supporting mass.

Then, carry out with embodiment 1 in identical step until forming charge generation layer.

Then, by preparing the charge transport layer coating fluid in the solvent mixture that 4 parts of compounds (charge transport material) by above-mentioned formula (4-1) expression, 6 parts is dissolved in dimethoxymethane (20 parts) and monochloro-benzene (60 parts) by the compound (charge transport material) of above-mentioned formula (CTM-1) expression and 10 parts of vibrin A1 (resin glue) synthetic in synthesis example 1.

The charge transport layer coating fluid is applied on the charge generation layer by dip-coating, and descended dry 1 hour, thereby acquisition has the charge transport layer of 10 μ m film thicknesses at 120 ℃.

For picture appraisal electrophotographic photosensitive element by use laser jet P1006 printer (making) by Hewlett-PackardDevelopment Company.It is that 5% test pattern is estimated in following environment that use has the printing rate: 23 ℃ of temperature and relative humidity 50%.When each output device had 1 of image formed thereon, the rotation that stops electrophotographic photosensitive element driving.In this way, estimate 1,000 image.As a result, picture quality is gratifying.

(embodiment 51 to 53)

Except the vibrin A1 that will be among the embodiment 50 uses changes into above-mentioned vibrin B1 (embodiment 51), above-mentioned vibrin H (embodiment 52) and the above-mentioned vibrin L (embodiment 53), with embodiment 50 in identical mode make electrophotographic photosensitive element.

Estimate in the mode identical with embodiment 50.In all cases, picture quality all is gratifying.

(embodiment 54)

The aluminium cylinder that will have diameter and be 30mm and length and be 357.5mm is as supporting mass.

Then, by preparing the charge transport layer coating fluid in the solvent mixture that 1 part of compound (charge transport material) by above-mentioned formula (4-1) expression, 9 parts is dissolved in dimethoxymethane (20 parts) and monochloro-benzene (60 parts) by the compound (charge transport material) of above-mentioned formula (CTM-1) expression and 10 parts of vibrin A1 (resin glue) synthetic in synthesis example 1.

The charge transport layer coating fluid is applied on the charge generation layer by dip-coating, and descended dry 1 hour, thereby form charge transport layer with 30 μ m film thicknesses at 120 ℃.

For the picture appraisal electrophotographic photosensitive element that passes through to use the iR3045 that makes by Canon Inc..It is that 5% test pattern is estimated in following environment that use has the printing rate: 23 ℃ of temperature and relative humidity 50%.When each output device had 1 of image formed thereon, the rotation that stops electrophotographic photosensitive element driving.In this way, estimate 1,000 image.As a result, picture quality is gratifying.

(embodiment 55 to 57)

Except the vibrin A1 that will be among the embodiment 54 uses changes into above-mentioned vibrin B1 (embodiment 55), above-mentioned vibrin H (embodiment 56) and the above-mentioned vibrin L (embodiment 57), with embodiment 54 in identical mode make electrophotographic photosensitive element.

Estimate in the mode identical with embodiment 54.In all cases, picture quality all is gratifying.

The right of priority of the Japanese patent application 2008-187180 that the application's request on July 18th, 2008 submits to, and its content introduced with for referencial use as the application's a part.

Claims

1. electrophotographic photosensitive element, it comprises supporting mass, be arranged at the charge generation layer on the described supporting mass and be formed at the charge transport layer that contains charge transport material and resin glue on the described charge generation layer, described charge transport layer is as superficial layer, and described electrophotographic photosensitive element is characterised in that:

Described charge transport layer contain have by the constitutional repeating unit of following formula (1) expression and by the vibrin of the constitutional repeating unit of following formula (2) expression as resin glue;

With respect to the gross mass of described vibrin, the content at siloxane position is for being not less than 5 quality % to being not more than 30 quality % in the described vibrin; With

With respect to whole gross mass of resin glues in the described charge transport layer, the content of vibrin described in the described charge transport layer is for being not less than 60 quality %,

2. electrophotographic photosensitive element according to claim 1, wherein with respect to whole gross mass of resin glues in the described charge transport layer, at the content at siloxane position described in the described charge transport layer for being not less than 5 quality % to being not more than 30 quality %.

3. electrophotographic photosensitive element according to claim 1 and 2, wherein the n in described formula (1) is to below 70 more than 25.

4. according to each described electrophotographic photosensitive element of claim 1 to 3, wherein with respect to the gross mass of whole resin glues in the described charge transport layer, the content at siloxane position described in the described charge transport layer is for being not less than 10 quality % to being not more than 25 quality %.

5. according to each described electrophotographic photosensitive element of claim 1 to 4, the wherein X in described formula (1) ¹For by following formula (3-12) or (3-13) expression structure and the X in described formula (2) ²For by following formula (3-12) or (3-13) expression structure:

6. according to each described electrophotographic photosensitive element of claim 1 to 5, wherein said charge transport layer comprises by the compound of following formula (4) expression as the charge transport material:

Wherein, in formula (4), Ar ¹To Ar ⁴Expression independently of one another replaces or unsubstituted aryl; Ar ⁵And Ar ⁶Expression independently of one another replaces or unsubstituted arlydene.

7. handle box, it comprises according to each described electrophotographic photosensitive element of claim 1-6 and at least a device that is selected from the group of being made up of charging device, developing apparatus, transfer device and cleaning device, and wherein said electrophotographic photosensitive element and described at least a device are supported integratedly and removably be mounted to the main body of electronic photographing device.

8. electronic photographing device, it comprises according to each described electrophotographic photosensitive element of claim 1-6, charging device, exposure device, developing apparatus and transfer device.